Cosmetic composition for coating keratin fibres

ABSTRACT

The present invention relates to a cosmetic composition for coating keratin fibers, comprising:—an aqueous phase,—a surfactant system present at a total content of greater than or equal to 15% by weight relative to the total weight of the composition, said surfactant system comprising: i) at least one non-ionic surfactant with an HLB value at 25° C. of less than 8, and ii) at least one anionic surfactant with an HLB value at 25° C. of greater than or equal to 8, chosen from acyl glutamic acids and salts thereof, together forming a lamellar phase Lβ, and—at least one aqueous dispersion of particles of at least one film-forming polymer. The present invention also relates to a process for coating keratin fibers.

The present invention relates to a cosmetic composition for coatingkeratin fibres, and in particular the eyelashes or the eyebrows. Inparticular, said cosmetic composition is a composition for making up andoptionally caring for the eyelashes. The present invention also relatesto a process for coating keratin fibres, in particular a process formaking up and optionally caring for the eyelashes. The present inventionalso relates to particular uses.

The composition used may in particular be in the form of an eyelashproduct such as a mascara, or an eyebrow product. More preferentially,the invention relates to a mascara. The term “mascara” is intended tomean a composition intended to be applied to the eyelashes: it may be aneyelash makeup composition, an eyelash makeup base (also known as a basecoat), a composition to be applied over a mascara, also known as a topcoat, or else a cosmetic composition for treating the eyelashes. Themascara is more particularly intended for human eyelashes, but also forfalse eyelashes.

Mascaras conventionally comprise a not insignificant amount of waxes andare commonly prepared according to two types of formulation: water-basedmascaras known as cream mascaras, in the form of a dispersion of waxesin water; anhydrous mascaras or mascaras with a low water content, knownas waterproof mascaras, in the form of dispersions of waxes in organicsolvents.

The present patent application more specifically relates to“water-based” mascaras.

The application of mascara is in particular directed towards increasingthe volume of the eyelashes and consequently increasing the intensity ofthe gaze. Numerous thickening or volumizing mascaras exist to do this,the principle of which consists in depositing a maximum amount ofmaterial onto the eyelashes so as to obtain this volumizing (orcharging) effect. It is in particular by means of the amount ofparticles (in particular waxes) that the desired applicationspecificities for the compositions may be adjusted, for instance theirfluidity or consistency, and also their thickening power (also known asthe charging or makeup power).

However, firstly, it proves to be the case that the change in texture ofa conventional mascara composition comprising waxes can sometimes bedifficult to control and totally unacceptable in terms of product,sometimes becoming solid after two months at 45° C., and thus no longerbe applicable.

This problem is in particular encountered with the conventionalformulation routes for aqueous mascaras which do not allow a high solidscontent, for example greater than or equal to 42%, to be exceeded,otherwise the texture is too thick.

Application EP 1 920 759 proposes structuring mascara compositions usingwaxes, in order to obtain a thick texture and a volumizing deposit. Inorder to homogeneously disperse these waxes, a system of specificsurfactants must be used, comprising an alkyl phosphate and an ether offatty alcohol and of polyethylene glycol having an HLB of strictly lessthan 8. Said application illustrates several examples of mascaracompositions comprising 20.14% by weight of waxes, for at most 10% bytotal weight of surfactants, relative to the total weight of thecomposition, with the surfactants essentially acting as an emulsifierfor these waxes.

Application FR 2 960 151, for its part, proposes promoting the wear andthe resistance to crumbling by using a specific surfactant systemcomprising an alkyl phosphate and an ether of fatty alcohol and ofpolyethylene glycol having an HLB of strictly less than 8, combined witha specific waxy phase. Said application illustrates several examples ofmascara compositions comprising more than 25.59% by weight of waxes,emulsified by means of the abovementioned surfactant system.

An aim of the present invention is thus to obtain a novel formulationroute for a mascara having improved stability over time and/or withrespect to temperature, for example stable for 2 months at 45° C.

An aim of the present invention is more particularly to provide amascara preferably with a high solids content, for example greater thanor equal to 42%.

More particularly, an aim of the present invention consists instabilizing a mascara without phase separation over time and/or withrespect to UV radiation and/or with respect to light.

An aim of the present patent application is more particularly to providea stable mascara, which has a texture that is thick enough to obtain acharging deposit, of satisfactory consistency, allowing easy applicationto the eyelashes and an even deposit, i.e. a deposit which is uniform,preferably even after two months stored at 4° C.

An aim of the present patent application is also to provide a stablemascara, which has a texture that is thick enough to obtain a chargingdeposit, of satisfactory consistency, allowing easy application to theeyelashes and an even deposit, i.e. a deposit which is uniform,preferably even after two months stored at 45° C.

An aim of the present patent application is more particularly to providea stable mascara, which has a texture that is thick enough to obtain acharging deposit, of satisfactory consistency, allowing easy applicationto the eyelashes and an even deposit, i.e. a deposit which is uniform,preferably even after two months stored at temperatures oscillatingbetween 4° C. and 45° C.

Moreover, it is known practice to use high weight contents of polymerparticles with the aim of making the deposit on the eyelashwater-resistant. The majority of smudge-proof mascaras are prepared inthis way. However, such compositions are not very pleasant uponapplication since the playtime is short: the number of brushstrokesremains limited, and the application becomes difficult after severalbrushstrokes. The combining of lamellar phases Lβ with particles offilm-forming polymers makes it possible to produce textures that arepleasant upon application.

An aim of the present invention is thus to provide a mascara which makesit possible to increase the “playtime” period, in particular to be ableto superimpose the layers with a number of brushstrokes greater than orequal to 20, better still greater than or equal to 30.

An aim of the present patent application is more particularly to providea mascara in which the pigments are uniformly dispersed.

An aim of the present patent application is more particularly to providea mascara that is pleasant upon application.

An aim of the present invention is also to obtain a composition forcoating keratin fibres, preferably a mascara, which produces avolumizing effect on the eyelashes, this preferably being despite thepresence of a low amount of waxes, or even this being despite theabsence of waxes.

An aim of the present invention is also to obtain a composition forcoating keratin fibres, preferably a mascara, which produces a chargingor covering deposit.

An aim of the present invention is also to obtain a composition forcoating keratin fibres, preferably a mascara, which has good lengtheningproperties for the eyelashes coated with such a composition.

An aim of the present invention is also to obtain a composition forcoating keratin fibres, preferably a mascara, which has good curlingproperties for the eyelashes coated with such a composition.

An aim of the present invention is also to obtain a composition forcoating keratin fibres, preferably a mascara, which has good adhesion onthe eyelashes.

Consequently, a subject of the present invention is a cosmeticcomposition for coating keratin fibres, preferably the eyelashes,preferably a mascara composition of the continuous aqueous phase type,comprising:

-   -   an aqueous phase,    -   a surfactant system present at a total content of greater than        or equal to 15% by weight relative to the total weight of the        composition, said surfactant system comprising:        -   i) at least one non-ionic surfactant with an HLB value at            25° C. of less than 8, and        -   ii) at least one anionic surfactant with an HLB value at            25° C. of greater than or equal to 8, chosen from acyl            glutamic acids and salts thereof, together forming a            lamellar phase Lβ, and    -   at least one aqueous dispersion of particles of at least one        film-forming polymer, the film-forming polymer(s) preferably        being present in a solids content of greater than or equal to 5%        by weight and preferably greater than or equal to 10% by weight        relative to the total weight of said composition,    -   it preferably being understood that said composition may        comprise at least one wax, the wax(es), when present, being        however present in a total content of strictly less than 10% by        weight relative to the total weight of the composition.

Surprisingly and unexpectedly, the inventors of the present patentapplication have solved this (these) problem(s) by means of such acomposition. In particular, a composition in accordance with theinvention gives rise to a composition which may be rich in solids, inparticular in particles such as in filler(s) and/or in pigment(s), andstable, having a uniform and even dispersion of particles, even after 2months, whether at 45° C. or at 4° C. It appears that such a compositionhas an intense black colour. Such a composition is still pleasant uponapplication, comfortable and has a volumizing effect. In addition to areinforced water resistance, this composition has an improved playtimedespite the presence of particles of film-forming polymer(s).

According to the inventors, a lamellar phase Lβ as described aboveallows an excellent compromise between texture and cosmeticity,conferring a charging effect which is stable over time, even after 2months, whether at 45° C. or at 4° C., optionally while dispensing withwax(es) which are nevertheless conventionally used in mascara to obtaina good charging effect. This new formulation route thus makes itpossible, surprisingly, to abandon the use of waxes, which arenevertheless conventional in a mascara. Furthermore, this lamellar phaseLβ allows, surprisingly, an improved “playtime”, even in the presence ofa dispersion of particles of film-forming polymer(s).

A surfactant system in accordance with the invention may optionallyessentially consist of, or even may consist of:

-   -   i) at least one non-ionic surfactant with an HLB value at 25° C.        of less than 8, and    -   ii) at least one anionic surfactant with an HLB value at 25° C.        of greater than or equal to 8, chosen from acyl glutamic acids        and salts thereof, together forming a lamellar phase Lβ.

According to a second aspect, a subject of the present invention is alsoan assembly or kit for coating keratin fibres, comprising:

-   -   at least one cosmetic composition for coating keratin fibres as        described previously, and    -   at least one applicator for the composition, said applicator        comprising means, where appropriate with reliefs, configured to        come into contact with said keratin fibres, such as the        eyelashes or the eyebrows, so as to smooth and/or separate the        eyelashes or the eyebrows. Such reliefs may comprise teeth,        bristles or the like. Said assembly, and in particular said        applicator, may optionally be equipped with means for vibrating        and/or heating said composition.

According to a third aspect, a subject of the present invention is alsoan assembly or kit for packaging and applying a composition for coatingkeratin fibres, comprising:

-   -   a device for packaging said cosmetic composition for coating        keratin fibres as described previously,    -   an applicator for said composition.        Said applicator may be integrally attached to a gripping member        forming a cap for said packaging device. In other words, said        applicator may be mounted in a removable position on said device        between a closed position and an open position of a dispensing        aperture of the device for conditioning said composition.

According to a fourth aspect, a subject of the present invention is alsoa process for coating keratin fibres, in particular for making up theeyelashes, comprising a step of applying a cosmetic coating compositionas defined previously.

According to particular preferred embodiments of the present inventionconcerning both the compositions and the processes described above anddirected towards solving at least one of the abovementioned problems:

-   -   the aqueous phase represents from 30% to 70% by weight and        preferably from 40% to 60% by weight relative to the total        weight of the composition;    -   the composition has a continuous aqueous phase;    -   the at least one from among the non-ionic surfactant(s) with an        HLB value of less than 8 is chosen from:        -   esters and ethers of monosaccharides which are optionally            (poly)oxyalkylenated, preferably (poly)oxyalkylenated;        -   esters of fatty acids, in particular of C₈-C₂₄ and            preferably of C₁₆-C₂₂ fatty acids, and of polyol, which is            optionally (poly)oxyalkylenated, preferably            (poly)oxyalkylenated, in particular of (poly)oxyalkylenated            glycerol or of oxyalkylenated sorbitol, preferably of            (poly)oxyalkylenated glycerol;        -   alcohols which are optionally (poly)oxyalkylenated,            preferably (poly)oxyalkylenated;        -   and mixtures thereof; preferably from among alcohols which            are optionally (poly)oxyalkylenated, preferably            (poly)oxyalkylenated;    -   the at least one from among the non-ionic surfactant(s) with an        HLB value at 25° C. of less than 8 comprises an alcohol which is        optionally (poly)oxyalkylenated, preferably        (poly)oxyalkylenated, comprising an ether of a C₈-C₂₄ fatty        alcohol and of polyethylene glycol, said ether comprising from 1        to 10 and better still between 2 and 6 ethylene glycol units;    -   the anionic surfactant(s) with an HLB value at 25° C. of greater        than or equal to 8, preferably greater than or equal to 10,        chosen from acyl glutamic acids and salts thereof, comprise(s)        at least one acyl glutamic acid having at least one C₁₂-C₂₂ acyl        chain, salt(s) (glutamates) thereof, and a mixture or mixtures        thereof;    -   the acyl glutamic acid(s) (INCI name: acyl glutamic acid), salts        (glutamates) thereof, and mixtures thereof, is (are) chosen from        acyl glutamic acids having a C₁₂-C₂₂ acyl chain, and the salts        of an alkali metal such as Na, Li or K, preferably Na or K, the        salts of an alkaline-earth metal such as Mg or the ammonium        salts of said acids, and a mixture or mixtures thereof;    -   the acyl glutamic acid(s) (INCI name: acyl glutamic acid), salts        (glutamates) thereof, and mixtures thereof, is (are) chosen from        lauroyl glutamic acid, myristoyl glutamic acid, palmitoyl        glutamic acid, stearoyl glutamic acid, behenoyl glutamic acid,        olivoyl glutamic acid, cocoyl glutamic acid, and the salts of an        alkali metal such as Na, Li or K, preferably Na or K, the salts        of an alkaline-earth metal such as Mg or the ammonium salts of        said acids, and a mixture or mixtures thereof;    -   the acyl glutamic acid(s) is (are) chosen from the compounds        bearing the INCI names lauroyl glutamic acid, cocoyl glutamic        acid, sodium stearoyl glutamate, potassium lauroyl glutamate,        potassium cocoyl glutamate and sodium olivoyl glutamate, and a        mixture or mixtures thereof;    -   the non-ionic surfactant(s) with an HLB value at 25° C. of less        than 8, preferably corresponding to formula (I), is (are)        present in a content of greater than or equal to 5% by weight        relative to the total weight of the composition, preferably        between 7% and 30%, preferably between 10% and 20% by weight        relative to the total weight of the composition;    -   the anionic surfactant(s) with an HLB value at 25° C. of greater        than or equal to 8, preferably greater than or equal to 10,        chosen from acyl glutamic acids and salts thereof, is (are)        present in a content of greater than or equal to 5% by weight        relative to the total weight of the composition, preferably        between 7% and 30%, preferably between 10% and 20% by weight        relative to the total weight of the composition;    -   the non-ionic surfactant(s) with an HLB value at 25° C. of less        than 8, preferably corresponding to formula (I), and the anionic        surfactant(s) with an HLB value at 25° C. of greater than or        equal to 8, preferably greater than or equal to 10, chosen from        acyl glutamic acids and salts thereof, are present in a total        content of greater than or equal to 15%, in particular between        16% and 40%, preferably between 18% and 30% by weight, relative        to the total weight of the composition;    -   the non-ionic surfactant(s) with an HLB value at 25° C. of less        than 8, preferably corresponding to formula (I), and the anionic        surfactant(s) with an HLB value at 25° C. of greater than or        equal to 8, preferably greater than or equal to 10, chosen from        acyl glutamic acids and salts thereof, are present in a        respective total content such that the weight ratio of the        non-ionic surfactant(s) with an HLB value at 25° C. of less than        8 to the anionic surfactant(s) with an HLB value at 25° C. of        greater than or equal to 8, chosen from acyl glutamic acids and        salts thereof, ranges from 1/5 to 5, preferably from 1/3 to 3,        preferably from 2/3 to 3/2;    -   the film-forming polymer particles introduced in aqueous        dispersion form into said composition have in said composition a        mean size expressed as the volume-mean “effective” less than or        equal to diameter D[4.3] of less than or equal to 5 μm,        preferentially less than or equal to 2 μm, even more        preferentially less than or equal to 1 μm, for example between        0.01 and 5 μm, and more preferentially between 0.1 and 2 μm;    -   the particles of film-forming polymer(s) present in aqueous        dispersion form are present according to a content of greater        than or equal to 5% by weight, preferably greater than or equal        to 10% by weight, more preferentially between 10% and 30% by        weight, relative to the total weight of the composition;    -   the particles of film-forming polymer(s) present in aqueous        dispersion form are chosen from synthetic polymers, of radical        type or of polycondensate type, polymers of natural origin, and        mixtures thereof;    -   the particles of film-forming polymer(s) present in aqueous        dispersion form are chosen from acrylic polymer dispersions,        polyurethane dispersions, sulfopolyester dispersions, vinyl        dispersions, polyvinyl acetate dispersions, vinylpyrrolidone,        dimethylaminopropylmethacrylamide and        lauryldimethylpropylmethacrylamidoammonium chloride terpolymer        dispersions, dispersions of polyurethane/polyacrylic hybrid        polymers, dispersions of particles of core-shell type and        mixtures thereof, preferably from acrylic polymer dispersions,        dispersions of polyurethane/polyacrylic hybrid polymers, and        derivatives thereof, and a mixture or mixtures thereof,        preferentially from acrylic in particular styrene-acrylic,        polymer dispersions, and polyurethane, in particular        polyester-polyurethane, dispersions, and derivatives thereof,        and a mixture or mixtures thereof;    -   the total content of particles of film-forming polymer(s) and        the total content of surfactant system are such that the weight        ratio of the particles of film-forming polymer(s)/surfactant        system is less than or equal to 1.75, preferably less than or        equal to 1.5, in particular between 1/2 and 1.25;    -   the composition comprises at least one spherical filler; the        spherical filler(s) is (are) preferably chosen from:        -   silica powders;        -   powders of acrylic (co)polymers, and derivatives thereof, in            particular powders of acrylate (co)polymer, and derivatives            thereof;        -   polyurethane powders;        -   silicone powders;        -   polyamide powders;        -   and a mixture or mixtures thereof, preferably from powders            of acrylic (co)polymers, and derivatives thereof, in            particular powders of acrylate (co)polymer, polyurethane            powders, and a mixture or mixtures thereof;    -   the spherical filler(s) is (are) present in a total content of        greater than or equal to 5% by weight, relative to the total        weight of the composition, for example between 8% and 30% by        weight, preferably between 8% and 25% by weight, better still        between 10% and 20% by weight, relative to the total weight of        the composition;    -   the composition comprises at least one lamellar filler;        preferably the lamellar filler(s) is (are) chosen from talc,        natural or synthetic mica, certain silicas, clays such as        magnesium aluminium silicates, kaolin, bentone, calcium        carbonate and magnesium hydrogen carbonate, hydroxyapatite,        boron nitride, fluorphlogopite, an N-lauroyl lysine powder,        perlite powders and a mixture or mixtures thereof, even more        preferentially the lamellar filler(s) is (are) chosen from talc,        le mica, fluorphlogopite, clays such as magnesium aluminium        silicate, an N-lauroyl lysine powder, and a mixture or mixtures        thereof;    -   the lamellar filler(s) is (are) present in a total content of        greater than or equal to 5% by weight, relative to the total        weight of the composition, for example between 8% and 30% by        weight, preferably between 8% and 25% by weight, better still        between 10% and 20% by weight, relative to the total weight of        the composition;    -   the composition comprises a content of wax(es) strictly less        than 10% by weight relative to the total weight of the        composition, preferably less than or equal to 5% by weight,        better still less than or equal to 2% by weight, or even is free        of wax(es);    -   said composition is free of oil or organic solvent;    -   the composition comprises a content of oil or organic solvent        strictly less than 10% by weight relative to the total weight of        the composition, preferably less than or equal to 5% by weight,        better still less than or equal to 2% by weight, or even is free        of oil or organic solvent;    -   said composition comprises a solids content of greater than or        equal to 42%, preferentially greater than or equal to 45%, more        preferentially greater than or equal to 48%, or even greater        than or equal to 50% and advantageously less than 60%;    -   said composition comprises at least one water-soluble        film-forming polymer, more preferentially said composition is        free of water-soluble film-forming polymer;    -   said composition comprises at least one colorant chosen from one        or more pulverulent substance(s), preferably metal oxides, and        in particular iron oxides;    -   the metal oxide(s) is (are) preferably present in a content of        greater than or equal to 5% by weight relative to the total        weight of the composition, and advantageously inclusively        between 6% and 22% by weight relative to the total weight of the        composition;    -   said composition comprises at least one hydrophilic and/or        lipophilic gelling agent, preferably at least one hydrophilic        gelling agent;    -   said composition has a viscosity at 25° C. ranging from 5 to 50        Pa·s, in particular measured using a Rheomat RM100® machine;    -   said composition may be a makeup composition, a makeup base or        “base coat”, or a “top coat” composition to be applied onto a        makeup.

Other characteristics, properties and advantages of the presentinvention will emerge more clearly on reading the description and theexamples that follow.

Aqueous Phase

The composition according to the invention comprises an aqueous phase,which advantageously forms a continuous phase of the composition.

The term “composition with an aqueous continuous phase” is intended tomean that the composition has a conductivity, measured at 25° C., ofgreater than or equal to 23 μS/cm (microSiemens/cm), the conductivitybeing measured, for example, using an MPC227 conductimeter from MettlerToledo and an Inlab730 conductivity measuring cell. The measuring cellis immersed in the composition so as to remove the air bubbles thatmight be formed between the two electrodes of the cell. The conductivityreading is taken once the conductimeter value has stabilized. A mean isdetermined on at least three successive measurements.

The aqueous phase comprises water. It may also comprise at least onewater-soluble solvent.

In the present invention, the term “water-soluble solvent” denotes acompound that is liquid at ambient temperature and water-miscible.

The water-soluble solvents that may be used in the compositionsaccording to the invention may also be volatile.

Among the water-soluble solvents that may be used in the compositions inaccordance with the invention, mention may be made in particular oflower monoalcohols containing from 1 to 5 carbon atoms such as ethanoland isopropanol, and glycols containing from 2 to 8 carbon atoms such asethylene glycol, propylene glycol, 1,3-butylene glycol and dipropyleneglycol.

The aqueous phase (water and optionally the water-miscible solvent) isgenerally present in the composition according to the present patentapplication in a content ranging from 30% to 70% by weight relative tothe total weight of the composition, and preferably ranging from 40% to60% by weight relative to the total weight of the composition. Thisaqueous phase content includes not only the water originating from theaqueous dispersions of film-forming polymers, and, where appropriate,from the aqueous dispersions of hard waxes, in accordance with theinvention, but also, where appropriate, the water deliberately added tothe composition.

Solids Content

The composition according to the invention advantageously comprises asolids content of greater than or equal to 42%, in particular greaterthan or equal to 45%, or even greater than or equal to 48% andpreferentially greater than or equal to 50%, and advantageously lessthan 60%.

For the purposes of the present invention, the “solids content” denotesthe content of non-volatile matter.

The solids content (abbreviated as SC) of a composition according to theinvention is measured using a Halogen Moisture Analyzer HR 73 commercialhalogen desiccator from Mettler Toledo. The measurement is performed onthe basis of the weight loss of a sample dried by halogen heating, andthus represents the percentage of residual matter once the water and thevolatile matter have evaporated off.

This technique is fully described in the machine documentation suppliedby Mettler Toledo.

The measuring protocol is as follows:

Approximately 2 g of the composition, referred to hereinbelow as thesample, are spread out on a metal crucible, which is placed in thehalogen desiccator mentioned above. The sample is then subjected to atemperature of 120° C. until a constant weight is obtained. The wet massof the sample, corresponding to its initial mass, and the dry mass ofthe sample, corresponding to its mass after halogen heating, aremeasured using a precision balance.

The experimental error associated with the measurement is of the orderof plus or minus 2%.

The solids content is calculated in the following manner:Solids content(expressed as weight percentage)=100×(dry mass/wet mass).

A composition according to the invention comprises wax particles,film-forming polymer particles and at least one particular surfactantsystem.

Lamellar Phase Lβ

Thus, a subject of the present patent application is a compositioncontaining, in an aqueous medium, a surfactant system organised in theform of a lamellar phase Lβ, or paracrystalline phase Lβ, or lamellargel phase.

This composition is stable at ambient temperature of 25° C.

This composition is preferably characterized by a viscositypreferentially ranging from 5 to 50 Pa·s, measured at a ambienttemperature of 25° C. using a Rheomat RM 100® rheometer.

The term “lamellar gel phase” or “paracrystalline phase Lβ” is intendedto mean a phase in which the surfactant molecules and/or more generallythe molecules of amphiphilic compounds are organized in the form ofbimolecular layers spaced apart by aqueous leaflets. Within thebimolecular layers, the molecules are distributed in a hexagonalgeometry, their hydrocarbon-based chains are in a crystalline state andare oriented perpendicular to the plane of the bimolecular layers buthave no specific orientation relative to each other in the plane ofthese layers.

The paracrystalline phases Lβ are metastable phases in which the fattychains are in solid form and are arranged randomly relative to eachother, unlike the micellar, cubic and lamellar fluid paracrystallinephases (Lα) in which the fatty chains are in liquid form, and unlike thecrystalline phases in which the fatty chains are in solid form andoriented in an ordered manner relative to each other. The Applicant hasfound a particular surfactant system that makes it possible to obtain astable paracrystalline phase Lβ, and thus cosmetic compositions forcoating keratin fibres, in particular the eyelashes, which are stableand pleasant upon application using a particular system of surfactantsin particular contents.

To identify the lamellar gel phase or paracrystalline phase Lβ of thesurfactant system present in the composition of the invention, use maybe made of various techniques, and in particular the technique ofwide-angle and small-angle X-ray scattering.

Wide Angle X-Ray Scattering—WAXS and Small Angle X-Ray Scattering—SAXS

X-ray diagrams were recorded by a Mar345 image plate detector(Maresearch, Norderstedt, Germany), mounted on a FR591 rotary anodeX-ray generator (Brüker, Courtaboeuf, France), used at 50 kV and at 50mA. The monochromatic CuKα radiation (λ=1,541 Å) was focused with a 350μm focal spot at 320 mm by double reflection on an ellipticcross-section multilayer Montel mirror (Incoatec, Geesthacht, Germany).The beam was defined under vacuum by four motorized carbon-tungstenslits (JJ-Xray, Roskilde, Denmark) positioned in front of the mirror(500 μm). Four additional guard slits were placed at the focal pointwith a 220 mm slit separation. The flux after the output mica windowswas 3×10⁸ photons/s. A 2-mm diameter circular metal wire beam stop wasplaced in air at 150 mm after the sample, and the detector waspositioned at 360 mm. The X-ray diagrams were therefore recorded for arange of reciprocal spacing q=4π*sin θ/λ of 0.03-1.8 Å⁻¹, in which θ isthe scattering angle. The repetitive distances d=2π/q should be between200 Å and 3.5 Å. The samples were placed in 1.2-1.3 mm glass capillaries(Glas W. Müller, Germany) and introduced into a home-made capillaryholder which can accommodate up to 20 capillaries at controlledtemperature.

Surfactant System

The surfactant system used in a composition in accordance with theinvention and which makes it possible to obtain the formation of aparacrystalline phase of lamellar type (Lβ) comprises:

-   -   at least one non-ionic surfactant with an HLB value at 25° C. of        less than 8, and    -   at least one anionic surfactant with an HLB value at 25° C. of        greater than or equal to 8, chosen from acyl glutamic acids and        salts thereof.

According to one particular embodiment, a composition according to theinvention comprises a surfactant system comprising:

-   -   at least one non-ionic surfactant with an HLB value at 25° C. of        less than 8, and    -   at least one anionic surfactant with an HLB value at 25° C. of        greater than or equal to 8, chosen from acyl glutamic acids and        salts thereof,        the non-ionic surfactant(s) with an HLB value at 25° C. of less        than 8 corresponding to formula (I) below:        (ALK-[C(O)]_(a)—[O]_(b))_(c)—X  (I)        in which formula (I):    -   ALK is a C₇-C₂₃, preferably C₁₁-C₂₁ and more preferentially        C₁₅-C₁₉ alkyl group,    -   a and b are integers between 0 and 100, c is an integer between        1 and 100, in particular between 1 and 3, preferably equal to 1,        a and b preferably being equal to 0,    -   X is a (poly)oxyalkylene group optionally substituted and/or        terminated with a hydroxyl group, X preferably being an        oxyethylene group (CH₂CH₂O)_(n) or (OCH₂CH₂)_(n) in which n is        greater than or equal to 1, for example between 1 and 10, said        (poly)oxyalkylene group preferably being a polyethylene glycol        or being the result of at least one substitution of a hydroxyl        group, preferably chosen from (poly)glycerols.        The group X is preferably chosen from:

i) HO-(ALK-O)_(z)—CH2-CH[(OALK)_(y)—OH]—CH2-(O-ALK)_(x)-(*)

in which:

-   -   ALK, which may be identical or different, represent a C₁-C₆ and        in particular C₁-C₄ alkylene group, preferably ethylene,    -   x, y and z are an integer between 0 and 10, it being understood        that x+y+z is other than 0, x+y+z preferably being inclusively        between 1 and 10;

ii) H-(ALK-O)_(x)-(*) and H—(O-ALK)_(x)-(*), preferably isH—(O-ALK)_(x)-(*)

in which:

-   -   ALK, which may be identical or different, represent a C1-C6 and        in particular C1-C4 alkylene group, preferably ethylene,    -   x is an integer other than 0 and preferably between 1 and 10.        The non-ionic surfactant(s) with an HLB value at 25° C. of less        than 8 correspond(s) to formula (I′) below:        ALK-(O—CH₂—CH₂)_(n)—OH  (I′)        in which formula (I′):    -   ALK is a C₈-C₂₄, preferably C₁₂-C₂₂ and more preferentially        C₁₆-C₁₈ alkyl group,        n being an integer other than 0, between 1 and 10, better still        between 2 and 6.

The Griffin HLB (hydrophilic/lipophilic balance) value is defined in J.Soc. Cosm. Chem. 1954 (volume 5), pages 249-256. Reference may be madeto the Kirk-Othmer Encyclopedia of Chemical Technology, volume 22, p.333-432, 3rd edition, 1979, Wiley, for the definition of the emulsifyingproperties and functions of surfactants, in particular p. 347-377 ofthis reference.

The non-ionic surfactant(s) with an HLB value at 25° C. of less than 8,preferably corresponding to formula (I), is (are) present in a contentof greater than or equal to 5% by weight relative to the total weight ofthe composition, preferably between 7% and 30%, preferably between 10%and 20% by weight relative to the total weight of the composition.

The anionic surfactant(s) with an HLB value at 25° C. of greater than orequal to 8, preferably greater than or equal to 10, chosen from acylglutamic acids and salts thereof, is (are) present in a content ofgreater than or equal to 5% by weight relative to the total weight ofthe composition, preferably between 7% and 30%, preferably between 10%and 20% by weight relative to the total weight of the composition.

The non-ionic surfactant(s) with an HLB value at 25° C. of less than 8,preferably corresponding to formula (I), and the anionic surfactant(s)with an HLB value at 25° C. of greater than or equal to 8, chosen fromacyl glutamic acids and salts thereof, are present in a total content ofgreater than or equal to 15%, in particular between 16% and 40% byweight, better still between 18% and 30% by weight, relative to thetotal weight of the composition.

The non-ionic surfactant(s) with an HLB value at 25° C. of less than 8,preferably corresponding to formula (I), and the anionic surfactant(s)with an HLB value at 25° C. of greater than or equal to 8, chosen fromacyl glutamic acids and salts thereof, are present in a respective totalcontent such that the weight ratio of the non-ionic surfactant(s) withan HLB value at 25° C. of less than 8 to the anionic surfactant(s) withan HLB value at 25° C. of greater than or equal to 8, chosen from acylglutamic acids and salts thereof, ranges from 1/5 to 5, preferably from1/3 to 3, preferably from 2/3 to 3/2.

Non-Ionic Surfactant(s) with an HLB Value at 25° C. of Less than 8

The non-ionic surfactant(s) with an HLB value, in the Griffin sense, at25° C., of less than 8 may be advantageously chosen from:

-   -   esters and ethers of monosaccharides which are optionally        (poly)oxyalkylenated, preferably (poly)oxyalkylenated;    -   esters of fatty acids, in particular of C₈-C₂₄ and preferably of        C₁₆-C₂₂ fatty acids, and of polyol, which is optionally        (poly)oxyalkylenated, preferably (poly)oxyalkylenated, in        particular of (poly)oxyalkylenated glycerol or of        (poly)oxyalkylenated sorbitol, preferably of        (poly)oxyalkylenated glycerol;    -   alcohols which are optionally (poly)oxyalkylenated, preferably        (poly)oxyalkylenated;    -   and mixtures thereof; preferably from among alcohols which are        optionally (poly)oxyalkylenated, preferably        (poly)oxyalkylenated, preferably comprising from 1 to 10        oxyethylene units.        The term “(poly)oxyalkylenated” is intended to mean from 1 to 10        oxyethylene group (or units) and better still from 2 to 6        oxyethylene groups.

The at least one from among the non-ionic surfactant(s) with an HLBvalue at 25° C. of less than 8 preferably comprises an alcohol which isoptionally (poly)oxyalkylenated, preferably (poly)oxyalkylenated,comprising an ether of a C₈-C₂₄ fatty alcohol and of polyethyleneglycol, said ether comprising from 1 to 10 and better still between 2and 6 ethylene glycol units.

A composition according to the invention has a content of non-ionicsurfactant(s) with an HLB value, in the Griffin sense, at 25° C., ofless than 8, of greater than or equal to 5% by weight relative to thetotal weight of the composition, preferably between 7% and 30%,preferably between 10% and 20% by weight relative to the total weight ofthe composition.

Anionic Surfactant(s) with an HLB Value at 25° C. of Greater than orEqual to 8

A composition in accordance with the invention comprises at least oneanionic surfactant with an HLB value, in the Griffin sense, at 25° C.,of greater than or equal to 8, preferably greater than or equal to 10,chosen from acyl glutamic acids and salts thereof.

The term “acyl glutamic acid(s)” is intended to mean, in thedescription, acyl glutamic acid(s) and salt(s) thereof.

A composition according to the invention comprises at least one acylglutamic acid having at least one C₁₂-C₂₂ acyl chain, salt(s)(glutamates) thereof, and a mixture or mixtures thereof.

In particular, the acyl glutamic acid(s) (INCI name: acyl glutamicacid), salts (glutamates) thereof, and mixtures thereof, is (are) chosenfrom acyl glutamic acids having a C₁₂-C₂₂ acyl chain, and the salts ofan alkali metal such as Na, Li or K, preferably Na or K, the salts of analkaline-earth metal such as Mg or the ammonium salts of said acids, anda mixture or mixtures thereof.

More preferentially, the acyl glutamic acid(s) (INCI name: acyl glutamicacid), salts (glutamates) thereof, and mixtures thereof, is (are)preferably chosen from lauroyl glutamic acid, myristoyl glutamic acid,palmitoyl glutamic acid, stearoyl glutamic acid, behenoyl glutamic acid,olivoyl glutamic acid, cocoyl glutamic acid, and the salts of an alkalimetal such as Na, Li or K, preferably Na or K, the salts of analkaline-earth metal such as Mg or the ammonium salts of said acids, anda mixture or mixtures thereof.

Mention may be made in particular of the compounds bearing the INCInames lauroyl glutamic acid, cocoyl glutamic acid, sodium stearoylglutamate, potassium lauroyl glutamate, potassium cocoyl glutamate andsodium olivoyl glutamate, and a mixture or mixtures thereof.

Such compounds are sold under the name Amisoft by the company Ajinomotoand in particular under the references Amisoft CA, Amisoft LA, AmisoftHS 11 PF, Amisoft MK-11, Amisoft LK-11 and Amisoft CK-11, oralternatively sold by the company Keminova Italiana SRL.

As acyl glutamic acid salt(s), mention may also be made of disodiumhydrogenated tallow glutamate such as the product sold under thereference Amisoft HS-21 by the company Ajinomoto.

Mention may also be made of commercial mixtures of surfactantscomprising at least one acyl glutamic acid salt, for example the mixtureof acyl glutamate salts such as Amisoft LS-22 sold by Ajinomoto.

A composition according to the invention has a content of anionicsurfactant(s), and in particular of acyl glutamic acids and saltsthereof, of greater than or equal to 5% by weight relative to the totalweight of the composition, preferably between 7% and 30%, preferablybetween 10% and 20% by weight relative to the total weight of thecomposition.

Preferably, a composition in accordance with the invention is free ofalkyl phosphates and in particular is free of cetyl phosphate.

Preferably, a composition in accordance with the invention is free ofamphoteric surfactant(s).

Moreover, the surfactant system may comprise one or more co-surfactantschosen from fatty alcohols comprising from 10 to 26 carbon atoms, betterstill from 12 to 24 carbon atoms and even better still from 14 to 22carbon atoms. However, this (these) co-surfactant(s) is (are) notinvolved in the calculation of the total content of surfactant system inaccordance with the invention.

Film-Forming Polymer(s)

The composition according to the invention comprises at least oneaqueous dispersion of film-forming polymer particles and optionally atleast one additional film-forming polymer (not present in the form of anaqueous dispersion of particles, such as a water-soluble film-formingpolymer).

In the present patent application, the term “film-forming polymer” isintended to mean a polymer that is capable, by itself or in the presenceof an auxiliary film-forming agent, of forming a macroscopicallycontinuous deposit, and preferably a cohesive deposit, and even betterstill a deposit of which the cohesion and the mechanical properties aresuch that said deposit can be isolated and manipulated individually, forexample when said deposit is prepared by pouring onto a non-sticksurface such as a Teflon-coated or silicone-coated surface.

A composition according to the invention preferably comprises a totalsolids content of film-forming polymer(s) of greater than or equal to 5%by weight, preferably greater than or equal to 10% by weight, relativeto the total weight of the composition, and better still greater than orequal to 12% by weight, relative to the total weight of the composition.

A composition according to the invention preferably comprises a totalsolids content of film-forming polymer(s) ranging from 10% to 30% byweight and better still from 12% to 25% relative to the total weight ofthe composition.

The composition according to the invention preferably comprises morespecifically at least one aqueous dispersion of particles formed fromone or more film-forming polymers.

It may also comprise at least one water-soluble film-forming polymer.Thus, a composition may comprise at least one additional film-formingpolymer, different from the film-forming polymer particles present inaqueous dispersion form. The content of these “water-soluble” additionalfilm-forming polymer(s) is preferably less than or equal to 10% byweight relative to the total weight of the composition, even morepreferentially less than or equal to 5% by weight and better still lessthan or equal to 2% by weight relative to the total weight of thecomposition.

Film-Forming Polymer(s) in Aqueous Dispersion

Such a film-forming polymer present in said preparation of thecomposition in the form of particles in aqueous dispersion is generallyknown as a (pseudo)latex, i.e. a latex or psuedolatex. Techniques forpreparing these dispersions are well known to those skilled in the art.

A dispersion that is suitable for use in the invention may comprise oneor more types of particle, these particles possibly varying as regardstheir size, their structure and/or their chemical nature.

A composition according to the invention may comprise a total solidscontent of particles of film-forming polymer(s) in aqueous dispersionform of greater than or equal to 5% by weight, or even greater than orequal to 10% by weight, relative to the total weight of the composition.

Advantageously, a composition according to the invention comprises atotal solids content of particles of film-forming polymer(s) in aqueousdispersion form of greater than or equal to 12% by weight relative tothe total weight of the composition and preferably greater than or equalto 15% by weight relative to the total weight of the composition.

A composition according to the invention preferably comprises a totalsolids content of particles of film-forming polymer(s) ranging from 10%to 30% by weight and better still from 12% to 25% by weight relative tothe total weight of the composition.

The total content of particles of film-forming polymer(s) present inaqueous dispersion form is preferably greater than or equal to 20% byweight, preferentially greater than or equal to 30%, preferably greaterthan 40% by weight, relative to the total weight of the particles.

These particles may be of anionic, cationic or neutral nature and mayconstitute a mixture of particles of different natures.

Among the film-forming polymers that may be used in the composition ofthe present invention, mention may be made of synthetic polymers, offree-radical type or of polycondensate type, and polymers of naturalorigin, and mixtures thereof. In general, these polymers may bestatistical polymers, block copolymers of A-B type, of A-B-A or alsoABCD, etc. multiblock type, or even grafted polymers.

Free-Radical Film-Forming Polymer

The term “free-radical polymer” is intended to mean a polymer obtainedby polymerization of unsaturated and in particular ethylenicallyunsaturated monomers, each monomer being capable of homopolymerizing(unlike polycondensates).

The film-forming polymers of free-radical type may in particular beacrylic and/or vinyl homopolymers or copolymers.

The vinyl film-forming polymers may result from the polymerization ofethylenically unsaturated monomers containing at least one acid groupand/or esters of these acid monomers and/or amides of these acidmonomers.

Ethylenically unsaturated monomers containing at least one acid group ormonomer bearing an acid group that may be used include α,β-ethylenicunsaturated carboxylic acids such as acrylic acid, methacrylic acid,crotonic acid, maleic acid or itaconic acid. (Meth)acrylic acid andcrotonic acid are in particular used, and more particularly(meth)acrylic acid.

The esters of acid monomers are advantageously chosen from (meth)acrylicacid esters (also known as (meth)acrylates), in particular(meth)acrylates of an alkyl, in particular of a C₁-C₂₀ and moreparticularly C₁-C₈ alkyl, (meth)acrylates of an aryl, in particular of aC₆-C₁₀ aryl, and (meth)acrylates of a hydroxyalkyl, in particular of aC₂-C₆ hydroxyalkyl.

Among the alkyl (meth)acrylates that may be mentioned are methylmethacrylate, ethyl methacrylate, butyl methacrylate, isobutylmethacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate.

Among the hydroxyalkyl (meth)acrylates that may be mentioned arehydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethylmethacrylate and 2-hydroxypropyl methacrylate.

Among the aryl (meth)acrylates that may be mentioned are benzyl acrylateand phenyl acrylate.

The (meth)acrylic acid esters are in particular alkyl (meth)acrylates.

According to the present invention, the alkyl group of the esters may beeither fluorinated or perfluorinated, i.e. some or all of the hydrogenatoms of the alkyl group are substituted with fluorine atoms.

Mention may be made, as amides of the acid monomers, for example, of(meth)acrylamides and in particular N-alkyl(meth)acrylamides, inparticular N—(C₂-C₁₂ alkyl)(meth)acrylamides. Among theN-alkyl(meth)acrylamides that may be mentioned are N-ethylacrylamide,N-t-butylacrylamide and N-t-octylacrylamide.

The vinyl film-forming polymers may also result from thehomopolymerization or copolymerization of monomers chosen from vinylesters and styrene monomers. In particular, these monomers may bepolymerized with acid monomers and/or esters thereof and/or amidesthereof, such as those mentioned previously.

Examples of vinyl esters that may be mentioned are vinyl acetate, vinylneodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate.

Styrene monomers that may be mentioned include styrene andα-methylstyrene.

The list of monomers given is not limiting, and it is possible to useany monomer known to those skilled in the art included in the categoriesof acrylic and vinyl monomers (including monomers modified with asilicone chain).

Vinyl polymers that may also be used include silicone acrylic polymers.

Mention may also be made of polymers resulting from free-radicalpolymerization of one or more free-radical monomers inside and/orpartially at the surface of pre-existing particles of at least onepolymer chosen from the group consisting of polyurethanes, polyureas,polyesters, polyesteramides and/or alkyds. These polymers are generallyreferred to as “hybrid polymers”.

Polycondensate

As film-forming polymer of polycondensate type, mention may be made ofanionic, cationic, non-ionic or amphoteric polyurethanes, acrylicpolyurethanes, polyvinylpyrrolidone-polyurethanes,polyester-polyurethanes, polyether-polyurethanes, polyureas,polyurea/polyurethanes and silicone polyurethanes, and mixtures thereof.

The film-forming polyurethane may be, for example, an aliphatic,cycloaliphatic or aromatic polyurethane, polyurea/urethane or polyureacopolymer comprising, alone or as a mixture, at least one block chosenfrom:

-   -   a block of aliphatic and/or cycloaliphatic and/or aromatic        polyester origin, and/or    -   a branched or unbranched silicone block, for example        polydimethylsiloxane or polymethylphenylsiloxane, and/or    -   a block comprising fluoro groups.

The film-forming polyurethanes as defined in the invention may also beobtained from branched or unbranched polyesters or from alkydscomprising mobile hydrogens, which are modified by reaction with adiisocyanate and a difunctional organic compound (for example dihydro,diamino or hydroxyamino), also comprising either a carboxylic acid orcarboxylate group, or a sulfonic acid or sulfonate group, oralternatively a neutralizable tertiary amine group or a quaternaryammonium group.

Among the film-forming polycondensates, mention may also be made ofpolyesters, polyesteramides, fatty-chain polyesters, polyamides andepoxyester resins.

The polyesters may be obtained, in a known manner, by polycondensationof dicarboxylic acids with polyols, in particular diols.

The dicarboxylic acid may be aliphatic, alicyclic or aromatic. Examplesof such acids that may be mentioned include: oxalic acid, malonic acid,dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelicacid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid, sebacicacid, fumaric acid, maleic acid, itaconic acid, phthalic acid,dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid,1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid,2,5-norboranedicarboxylic acid, diglycolic acid, thiodipropionic acid,2,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid.These dicarboxylic acid monomers may be used alone or as a combinationof at least two dicarboxylic acid monomers. Among these monomers, theones chosen in particular are phthalic acid, isophthalic acid andterephthalic acid.

The diol may be chosen from aliphatic, alicyclic and aromatic diols. Thediol used is chosen in particular from: ethylene glycol, diethyleneglycol, triethylene glycol, 1,3-propanediol, cyclohexanedimethanol and4-butanediol. Other polyols that may be used are glycerol,pentaerythritol, sorbitol and trimethylolpropane.

The polyesteramides may be obtained in a manner analogous to that of thepolyesters, by polycondensation of diacids with diamines or aminoalcohols. Diamines that may be used are ethylenediamine,hexamethylenediamine and meta- or para-phenylenediamine. An aminoalcohol that may be used is monoethanolamine.

Polymer of Natural Origin

Use may be made in the present invention of optionally modified polymersof natural origin, such as shellac resin, sandarac gum, dammar resins,elemi gums, copal resins, water-insoluble cellulose-based polymers suchas nitrocellulose, modified cellulose esters in particular includingcarboxyalkyl cellulose esters such as those described in patentapplication US 2003/185 774, and mixtures thereof.

According to a particular embodiment of the invention, said at least onefilm-forming polymer in the dispersed state is chosen from acrylicpolymer dispersions, polyurethane dispersions, sulfopolyesterdispersions, vinyl dispersions, polyvinyl acetate dispersions,vinylpyrrolidone, dimethylaminopropylmethacrylamide andlauryldimethylpropylmethacrylamidoammonium chloride terpolymerdispersions, dispersions of polyurethane/polyacrylic hybrid polymers anddispersions of particles of core-shell type, and mixtures thereof.

Various types of aqueous dispersion, in particular commercial aqueousdispersions, which are suited to the preparation of the composition inaccordance with the present invention are detailed below.

1/ Thus, According to One Preferred Embodiment of the Invention, theAqueous Dispersion of Polymer Particles is an Aqueous Dispersion ofAcrylic Polymer.

The acrylic polymer can be a styrene/acrylate copolymer and inparticular a polymer chosen from copolymers resulting from thepolymerization of at least one styrene monomer and at least one C₁-C₁₈alkyl (meth)acrylate monomer.

As styrene monomer that may be used in the invention, examples that maybe mentioned include styrene and α-methylstyrene, and in particularstyrene.

The C₁-C₁₈ alkyl (meth)acrylate monomer is in particular a C₁-C₁₂ alkyl(meth)acrylate and more particularly a C₁-C₁₀ alkyl (meth)acrylate. TheC₁-C₁₈ alkyl (meth)acrylate monomer may be chosen from methyl acrylate,methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate,butyl methacrylate, hexyl acrylate, octyl acrylate, 2-ethylhexylacrylate, lauryl (meth)acrylate and stearyl (meth)acrylate.

As acrylic polymer in aqueous dispersion, use may be made according tothe invention of the styrene/acrylate copolymer sold under the nameJoncryl SCX-8211® by the company BASF or Syntran 5760CG by the companyInterpolymer, the acrylic polymer sold under the reference Acronal®DS-6250 by the company BASF, or the acrylic copolymer Joncryl® 95 by thecompany BASF.

2/ According to one embodiment variant of the invention, the aqueousdispersion of polymer particles is an aqueous dispersion ofpolyester-polyurethane and/or polyether-polyurethane particles, inparticular in anionic form.

The anionic nature of the polyester-polyurethanes and of thepolyether-polyurethanes used according to the invention is due to thepresence in their constituent units of groups bearing a carboxylic acidor sulfonic acid function.

The polyester-polyurethane or polyether-polyurethane particles usedaccording to the invention are generally sold in aqueous dispersionform.

The particle content of said dispersions currently available on themarket ranges from approximately 20% to approximately 60% by weightrelative to the total weight of the dispersion.

Among the anionic polyester-polyurethane dispersions that may be used inthe compositions according to the invention, mention may be made inparticular of the product sold under the name Avalure UR 405® by thecompany Noveon or Baycusan C1004 by the company Bayer Material Science.

Among the anionic polyether-polyurethane particle dispersions that maybe used according to the invention, mention may be made in particular ofthe products sold under the name Avalure UR 450® by the company Noveonand under the name Neorez R 970® by the company DSM.

According to a particular embodiment of the invention, use may be madeof a mixture of commercial dispersions consisting of anionicpolyester-polyurethane particles as defined above and of anionicpolyether-polyurethane particles also defined above.

For example, use may be made of a mixture consisting of the dispersionsold under the name Sancure 861® or a mixture of the product sold underthe name Avalure UR 405® and of the product sold under the name AvalureUR 450®, these dispersions being sold by the company Noveon.

3/ According to another particular embodiment of the invention, theaqueous dispersion used comprises a mixture of at least two film-formingpolymers in the form of particles that differ by their respective glasstransition temperatures (Tg).

In particular, according to one embodiment of the invention, thecomposition in accordance with the invention may comprise at least onefirst film-forming polymer in the dispersed state and at least onesecond film-forming polymer in the dispersed state, said first andsecond polymers having different Tg values and, preferably, the Tg ofthe first polymer (Tg1) is higher than the Tg of the second polymer(Tg2). In particular, the difference between the Tg1 and Tg2 values is,as an absolute value, at least 10° C. and preferably at least 20° C.

More precisely, it comprises in an acceptable aqueous medium:

a) particles dispersed in the aqueous medium of a first film-formingpolymer having at least one glass transition temperature Tg1 greaterthan or equal to 20° C., and

b) particles dispersed in the aqueous medium of a second film-formingpolymer having at least one glass transition temperature Tg1 less thanor equal to 70° C.

This dispersion generally results from a mixing of two aqueousdispersions of film-forming polymer.

The first film-forming polymer has at least one, and in particular hasone, glass transition temperature Tg1 greater than or equal to 20° C.,in particular ranging from 20° C. to 150° C. and advantageously greaterthan or equal to 40° C., in particular ranging from 40° C. to 150° C.and in particular greater than or equal to 50° C., in particular rangingfrom 50° C. to 150° C.

The second film-forming polymer has at least one, and in particular hasone, glass transition temperature Tg2 less than or equal to 70° C., inparticular ranging from −120° C. to 70° C., in particular less than 50°C., in particular ranging from −60° C. to +50° C. and more particularlyranging from −30° C. to 30° C.

The measurement of the glass transition temperature (Tg) of a polymer isperformed by DMTA (dynamic and mechanical temperature analysis) asdescribed below.

To measure the glass transition temperature (Tg) of a polymer,viscoelasticity tests are performed with a “Polymer Laboratories” DMTAmachine, on a sample of film. This film is prepared by pouring theaqueous dispersion of film-forming polymer in a Teflon-coated matrixfollowed by drying at 120° C. for 24 hours. A film is then obtained,from which specimens are cut out (for example using a punch). Thesespecimens are typically about 150 μm thick, from 5 to 10 mm wide andhave a useful length of about 10 to 15 mm. A tensile stress is imposedon this sample. The sample undergoes a static force of 0.01 N on whichis superimposed a sinusoidal displacement of ±8 μm at a frequency of 1Hz. The test is thus performed in the linear range, at low levels ofdeformation. This tensile stress is performed on the sample attemperatures ranging from −150° C. to +200° C., with a temperaturevariation of 3° C. per minute.

The complex modulus E*=E′+iE″ of the polymer tested is thus measured asa function of the temperature.

From these measurements, the dynamic moduli E′ and E″ and the dampingpower: tgδ=E″/E′ are deduced.

The curve of the tgδ values is then plotted as a function of thetemperature; this curve presents at least one peak. The glass transitiontemperature Tg of the polymer corresponds to the temperature at the topof this peak.

When the curve presents at least two peaks (in this case, the polymerpresents at least two Tg values), the value taken as the Tg of thepolymer tested is the temperature for which the curve presents a peak ofthe largest amplitude (i.e. corresponding to the largest tgδ value; inthis case, only the “major” Tg is considered as the Tg value of thepolymer tested).

In the present invention, the transition temperature Tg1 corresponds tothe “major” resents Tg (in the predefined sense) of the firstfilm-forming polymer when the latter presents at least two Tg values;the glass transition temperature Tg2 corresponds to the “major” presentsTg of the second film-forming polymer when the latter presents at leasttwo Tg values.

The first film-forming polymer and the second film-forming polymer maybe chosen, independently of each other, from free-radical polymers,polycondensates and polymers of natural origin as defined previouslyhaving the glass transition temperature characteristics definedpreviously.

As first film-forming polymer in aqueous dispersion, use may be made ofthe aqueous polymer dispersions sold under the names Neorez R-989® bythe company DSM, Joncryl 95 and Joncryl® 8211 by the company BASF.

As second film-forming polymer in aqueous dispersion, use may be made,for example, of the aqueous polymer dispersions sold under the namesAvalure® UR-405, Avalure® UR-460 by the company Noveon or AcrilemIC89RT® by the company ICAP, and Neocryl A-45 by the company DSM.

The film-forming polymer of the aqueous dispersion Avalure® UR-460 is apolyurethane obtained by polycondensation of polytetramethylene oxide,tetramethylxylylene diisocyanate, isophorone diisocyanate anddimethylolpropionic acid.

According to a most particularly preferred embodiment of the invention,use is made, as first and second film-forming polymers in aqueousdispersion, of the combination of styrene/acrylate polymer dispersionsuch as the dispersion sold under the reference Joncryl 8211® by BASFand of acrylic polymer dispersion such as the dispersion sold under thereference Neocryl A-45® by DSM.

According to another preferred embodiment of this particular embodimentof point 3/above of the invention, use is made, as first film-formingpolymer in aqueous dispersion, of an acrylic polymer dispersion such asthe dispersion sold under the reference Joncryl 95® by BASF and, assecond film-forming polymer, of a dispersion of anionic polyurethanepolymer sold under the reference Avalure UR405® by DSM.

As aqueous dispersions of film-forming polymer, use may be made of:

-   -   the acrylic dispersions sold under the names Acronal DS-6250® by        the company BASF, Neocryl A-45®, Neocryl XK-90®, Neocryl        A-1070®, Neocryl A-1090®, Neocryl BT-62®, Neocryl A-1079® and        Neocryl A-523® by the company DSM, Joncryl 95® and Joncryl 8211®        by the company BASF, Daitosol 5000 AD® or Daitosol 5000 SJ by        the company Daito Kasey Kogyo; Syntran 5760 CG by the company        Interpolymer,    -   the aqueous polyurethane dispersions sold under the names Neorez        R-981® and Neorez R-974® by the company DSM, Avalure UR-405®,        Avalure UR-410®, Avalure UR-425®, Avalure UR-450®, Sancure 875®,        Avalure UR 445® and Avalure UR 450® by the company Noveon,        Impranil 85® by the company Bayer, and Baycusan C1004® by the        company Bayer Material Science,    -   the sulfopolyesters sold under the brand name Eastman AQ® by the        company Eastman Chemical Products,    -   vinyl dispersions such as Mexomer PAM, aqueous dispersions of        polyvinyl acetate such as Vinybran® from the company Nisshin        Chemical or the products sold by the company Union Carbide,        aqueous dispersions of vinylpyrrolidone,        dimethylaminopropylmethacrylamide and        lauryldimethylpropylmethacrylamidoammonium chloride terpolymer        such as Styleze W® from ISP,    -   aqueous dispersions of polyurethane/polyacrylic hybrid polymer        such as the products sold under the references Hybridur® by the        company Air Products or Duromer® from National Starch,    -   dispersions of particles of core-shell type such as the products        sold by the company Arkema under the reference Kynar® (core:        fluorinated—shell: acrylic) or alternatively those described in        U.S. Pat. No. 5,188,899 (core: silica—shell: silicone), and        mixtures thereof.

According to a preferred embodiment, a composition in accordance withthe invention comprises an aqueous dispersion of particles chosen fromaqueous dispersions of acrylic film-forming polymer(s) and derivatives,in particular of styrene-acrylic film-forming polymer(s) andderivatives, and aqueous dispersions of polyurethane polymer(s), inparticular of polyester-polyurethane polymer(s), and derivativesthereof, and a mixture or mixtures thereof.

Water-Soluble Film-Forming Polymer

The compositions according to the present invention comprise at leastone water-soluble film-forming polymer.

Preferably, a composition according to the invention is free ofwater-soluble film-forming polymer. However, the total solids content of“water-soluble film-forming polymer(s)” may range from 0.1% to 10%,preferably from 0.5% to 8% and better still from 1% to 5% by weightrelative to the total weight of the composition.

Examples of water-soluble film-forming polymers that may be mentionedinclude:

-   -   proteins, for instance proteins of plant origin, such as wheat        proteins, soya proteins;    -   cellulose polymers such as hydroxyethyl cellulose, hydroxypropyl        cellulose, methyl cellulose, ethyl hydroxyethyl cellulose and        carboxymethyl cellulose, and also quaternized cellulose        derivatives;    -   acrylic polymers or copolymers, such as polyacrylates or        polymethacrylates;    -   vinyl polymers, such as polyvinylpyrrolidones, copolymers of        methyl vinyl ether and of malic anhydride, the copolymer of        vinyl acetate and of crotonic acid, copolymers of        vinylpyrrolidone and of vinyl acetate; copolymers of        vinylpyrrolidone and of caprolactam; polyvinyl alcohol;    -   anionic, cationic, amphoteric or non-ionic chitin or chitosan        polymers;    -   gum arabic, guar gum, xanthan derivatives, karaya gum, acacia        gum;    -   alginates and carrageenans;    -   glycoaminoglycans, hyaluronic acid and its derivatives;    -   deoxyribonucleic acid;    -   mucopolysaccharides such as chondroitin sulfates;    -   and mixtures thereof.

Fillers

A composition according to the invention may comprise at least onefiller.

The term “fillers” should be understood as meaning colourless or whitesolid particles of any form, which are in a form that is insoluble anddispersed in the medium of the composition. Mineral or organic innature, they make it possible to confer softness, mattness anduniformity of makeup on the composition.

The fillers may or may not be surface-coated, and in particular they maybe surface-treated with silicones, amino acids, fluoro derivatives orany other substance that promotes the dispersion and compatibility ofthe filler in the composition.

Such fillers are distinct from what is referred to in the next sectionas “colouring agents”.

A composition according to the invention advantageously has a fillercontent of greater than or equal to 5% by weight, better still greaterthan or equal to 8% by weight, relative to the total weight of thecomposition, advantageously between 8% and 30% by weight, better stillbetween 8% and 25% by weight, better still between 10% and 20% byweight, relative to the total weight of the composition.

The composition may comprise at least one filler chosen from lamellarfillers, spherical fillers and a mixture thereof.

Lamellar Fillers

The composition may comprise at least one lamellar filler.

The lamellar filler(s) that can be used in the compositions according tothe invention is (are) preferably chosen from talc, natural or syntheticmica, certain silicas, clays such as magnesium aluminium silicates,perlite particles, kaolin, bentone, calcium carbonate and magnesiumhydrogen carbonate, hydroxyapatite, boron nitride, fluorphlogopite, anN-lauroyl lysine powder, and a mixture or mixtures thereof.

Perlite Particles

Perlite is generally obtained from natural glass of volcanic origin, oflight-grey or glossy black colour, resulting from the rapid cooling oflava, and which is in the form of small particles resembling pearls.When heated above 800° C., perlite has the particular feature of losingthe water it contains and of adopting a porous expanded form(representing from four to twenty times its initial volume), enabling itto absorb large amounts of liquid, in particular of oil and water. Itthen has a white colour.

Perlite, which is of mineral origin, is directly extracted from theground and then finely ground to obtain a very fine white powder:perlite powder or perlite particles.

Perlite particles are thus particles of amorphous mineral materials,which are advantageously expanded, derived from at least one volcanicrock.

These particles comprise at least two elements chosen from silicon,aluminium and magnesium.

More particularly, these mineral materials are obtained by thermalexpansion of a volcanic or “effusive” rock comprising from 1% to 10% byweight of water and preferably 1% to 5% by weight of water and less than10% by weight of crystalline rock relative to the total weight of therock composition and preferably followed by grinding. The temperature ofthe expansion process may range from 700 to 1500° C. and preferably from800 to 1100° C. The expansion process described in U.S. Pat. No.5,002,698 may in particular be used.

Volcanic or “effusive” rocks are generally produced by the rapid coolingof liquid magma in contact with air or water (quenching phenomenongiving a hyaline rock). The volcanic rocks that may be used according tothe present invention are chosen from those defined according to theStreckeisen classification (1974). Among these volcanic rocks, mentionmay be made in particular of trachytes, latites, andesites, basalts,rhyolites and dacites. Rhyolites and dacites are particularly suitablefor use, and even more particularly rhyolites.

The perlite particles that may be used according to the invention arepreferably aluminosilicates of volcanic origin. They advantageously havethe following composition:

70.0-75.0% by weight of silica SiO₂

12.0-15.0% by weight of aluminium oxide Al₂O₃

3.0-5.0% of sodium oxide Na₂O

3.0-5.0% of potassium oxide K₂O

0.5-2% of iron oxide Fe₂O₃

0.2-0.7% of magnesium oxide MgO

0.5-1.5% of calcium oxide CaO

0.05-0.15% of titanium oxide TiO₂

In the implementation of the present invention, the perlite undergoes afirst milling step so as to form perlite particles, and is dried andthen calibrated. The product obtained, known as perlite ore, isgrey-coloured and has a size of the order of 100 μm. The perlite ore issubsequently expanded (1000° C./2 seconds) to give more or less whiteparticles. When the temperature reaches 850-900° C., the water trappedin the structure of the material evaporates and brings about theexpansion of the material, with respect to its original volume. Theexpanded perlite particles in accordance with the invention may beobtained via the expansion process described in patent U.S. Pat. No.5,002,698.

Preferably, the perlite particles used are then milled in a secondmilling step in order further to reduce the size of the perliteparticles used; in this case, they are referred to as expanded milledperlite (EMP). They preferably have a particle size defined by a mediandiameter D₅₀ ranging from 0.5 to 50 μm and preferably from 1 to 40 μm.

Preferentially, the perlite particles have a platelet shape; they areconsequently usually called lamellar fillers, as opposed to sphericalfillers, of globular shape.

The perlite particles advantageously have a coefficient of expansion offrom 2 to 70.

Preferentially, the perlite particles have an untamped density at 25° C.ranging from 10 to 400 kg/m₃ (standard DIN 53468) and preferably from 10to 300 kg/m³.

According to one particular embodiment of the invention, the perliteparticles have a silica content of greater than or equal to 65% byweight relative to the total weight of the composition of the material.According to one particular embodiment of the invention, the perliteparticles have a spontaneous pH, measured at 25° C. in a dispersion inwater at 10% by weight, ranging from 6 to 8.

Preferably, the expanded perlite particles according to the inventionhave a water absorption capacity, measured at the wet point, rangingfrom 200% to 1500% and preferably from 250% to 800%.

The perlite particles used according to the invention are in particularcommercially available from the company World Minerals under the tradename Perlite P1430, Perlite P2550, Perlite P2040 or OpTiMat™ 1430 OR or2550 OR.

As representatives of such fillers preferably used in the context of thepresent invention, mention may be made in particular of: talc, mica,fluorphlogopite, perlite, clays such as magnesium aluminium silicate, anN-lauroyl lysine powder, and a mixture or mixtures thereof.

The lamellar filler(s) is (are) advantageously present in a compositionin accordance with the present invention in a total content of greaterthan or equal to 5% by weight, relative to the total weight of thecomposition, for example between 8% and 30% by weight, relative to thetotal weight of the composition, preferably between 8% and 25% byweight, better still between 10% and 20% by weight.

Spherical Fillers

The term “spherical fillers” should be understood to mean fillerscomprising at least one rounded general portion, preferably defining atleast one sphere portion, preferably defining internally a cavity or ahollow.

Such fillers referred to as spherical may be perfectly sphericalfillers, globular fillers, hemi-spherical fillers, bowl-shaped fillersor else horseshoe-shaped fillers.

The spherical filler(s) is (are) preferably hollow, where appropriatebeing capable of absorbing and/or adsorbing at least partially the oilyphase and more generally the fatty phase.

The spherical filler(s) in accordance with the invention is (are)advantageously a sebum-absorbing particle or particles, having a sebumuptake. The term “sebum-absorbing particle” is intended to mean a powdercapable of absorbing and/or adsorbing sebum.

The sebum uptake corresponds to the amount of sebum absorbed and/oradsorbed by the particle. It is measured according to the wet pointmethod as follows:

Method for Measuring Sebum Uptake of a Powder:

The sebum uptake of a powder is measured according to the method fordetermining the oil uptake of a powder described in standard NF T30-022. It corresponds to the amount of sebum adsorbed onto theavailable surface of the powder, by measuring the wet point.

An amount m (in grams) of powder of between about 0.5 g and 5 g (theamount depends on the density of the powder) is placed on a glass plateand artificial sebum having the following composition is then addeddropwise:

triolein  29% oleic acid 28.5% oleyl oleate 18.5% squalene  14%cholesterol   7% cholesteryl palmitate   3%

After addition of 4 to 5 drops of artificial sebum, the artificial sebumis incorporated into the powder using a spatula, and addition of theartificial sebum is continued until conglomerates of artificial sebumand powder have formed. From this point, the artificial sebum is addedat a rate of one drop at a time and the mixture is subsequentlytriturated with the spatula. The addition of artificial sebum is stoppedwhen a firm, smooth paste is obtained. This paste must be able to bespread on the glass plate without cracking or forming lumps. The volumeVs (expressed in ml) of artificial sebum used is then noted.

The sebum uptake corresponds to the ratio Vs/m.

Advantageously, the spherical fillers in accordance with the inventionhave a sebum uptake greater than or equal to 10 ml/100 g, in particulargreater than or equal to 20 ml/100 g, and in particular greater than orequal to 30 ml/100 g, preferably greater than or equal to 40 ml/100 g,and in particular inclusively between 45 and 1500 ml/100 g, or elsebetween 45 and 300 ml/100 g.

The spherical filler(s) advantageously has (have) an average diameter,also called median diameter or number-average size, indicated by a valueD₅₀, ranging from 0.05 μm to 50 μm, preferably ranging from 2 to 40 μm.This dimension D₅₀ is given by the statistical particle sizedistribution at half the population, termed D50. The spherical filler(s)may be present in a total content of greater than or equal to 5% byweight, relative to the total weight of the composition, for examplebetween 8% and 30% by weight, relative to the total weight of thecomposition, preferably between 8% and 25% by weight, better stillbetween 10% and 20% by weight.

The spherical filler(s) may be present in a total content of greaterthan or equal to 5% by weight, relative to the total weight of thecomposition, for example between 8% and 30% by weight, relative to thetotal weight of the composition, preferably between 8% and 25% byweight, better still between 10% and 20% by weight.

The filler(s) and the surfactant system in accordance with the inventionare advantageously present in a respective total weight content suchthat the weight ratio of the filler(s) to the surfactant system isgreater than or equal to 1/10, preferably between 1/5 and 6/5.

The filler(s) and the anionic surfactant(s) with an HLB value of greaterthan or equal to 8 are advantageously present in the composition in arespective total content such that the weight ratio of the filler(s) tothe anionic surfactant(s) with an HLB value of greater than or equal to8 ranges from 1/20 to 1, preferably from 1/10 to 2/3.

The filler(s) and the non-ionic surfactant(s) with an HLB value of lessthan 8 are advantageously present in the composition in a respectivetotal content such that the weight ratio of the filler(s) to thenon-ionic surfactant(s) with an HLB value of less than 8 ranges from1/20 to 1, preferably from 1/10 to 2/3.

The spherical fillers may be inorganic or organic, preferably organic.

As non-limiting illustrations of fillers, mention may be made mostparticularly of the particles below.

The spherical fillers are advantageously chosen from:

-   -   silica powders;    -   powders of acrylic (co)polymers, and derivatives thereof, in        particular powders of acrylate (co)polymer, and derivatives        thereof, advantageously chosen from a polymethyl methacrylate        powder, a polymethyl methacrylate/ethylene glycol dimethacrylate        powder, a polyallyl methacrylate/ethylene glycol dimethacrylate        powder, an ethylene glycol dimethacrylate/lauryl methacrylate        copolymer powder, a powder of acrylate/alkyl acrylate copolymer        which is optionally crosslinked, expanded hollow particles of        acrylonitrile (co)polymer, and a mixture or mixtures thereof;    -   polyurethane powders;    -   silicone powders advantageously chosen from a        polymethylsilsesquioxane powder, an organopolysiloxane elastomer        powder coated with silicone resin, a powder of organosilicone        particles;    -   powders of polyamides, such as Nylon®, in particular Nylon 12.

Such spherical fillers may be coated with a hydrophobic treatment agent.The hydrophobic treatment agent can be chosen from fatty acids, such asstearic acid; metal soaps, such as aluminium dimyristate or thealuminium salt of hydrogenated tallow glutamate; amino acids;N-acylamino acids or their salts; lecithin, isopropyl-triisostearyltitanate, and mixtures thereof. The N-acylamino acids can comprise anacyl group containing from 8 to 22 carbon atoms, for instance a2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl orcocoyl group. The salts of these compounds can be the aluminium,magnesium, calcium, zirconium, zinc, sodium or potassium salts. Theamino acid can, for example, be lysine, glutamic acid or alanine. Theterm “alkyl” mentioned in the compounds cited above denotes inparticular an alkyl group having from 1 to 30 carbon atoms andpreferably having from 5 to 16 carbon atoms.

More particularly, the spherical filler(s) is (are) advantageouslychosen from powders of acrylic (co)polymers, and derivatives thereof, inparticular a polymethyl methacrylate powder, polyurethane powders, inparticular a hexamethylene diisocyanate/trimethylol hexyl lactonecopolymer powder, and a mixture or mixtures thereof.

Silica Powders

Mention may be made, as silica powder, of:

-   the porous silica microspheres sold under the name Silica Beads    SB-700 by the company Miyoshi; Sunsphere® H51, Sunsphere® H33 by the    company Asahi Glass;-   the polydimethylsiloxane-coated amorphous silica microspheres sold    under the name SA Sunsphere® H33 or SA Sunsphere® H53 by the company    Asahi Glass.

Powders of Acrylic (Co)Polymers, and Derivatives Thereof

Mention may be made, as acrylic (co)polymer powder, and in particularacrylate (co)polymer powder, of:

-   -   the polymethyl methacrylate powders sold under the name        Covabead® LH85 by the company Wackherr;    -   the polymethyl methacrylate/ethylene glycol dimethacrylate        powders sold under the name Dow Corning 5640 Microsponge® Skin        Oil Adsorber by the company Dow Corning and the name Ganzpearl®        GMP-0820 by the company Ganz Chemical;    -   the polyallyl methacrylate/ethylene glycol dimethacrylate        powders sold under the names Polypore® L200 and Polypore® E200        by the company Amcol Health and Beauty Solutions Inc.;    -   the ethylene glycol dimethacrylate/lauryl methacrylate copolymer        powders sold under the name Polytrap® 6603 by the company Dow        Corning;    -   the crosslinked acrylate/ethylhexyl acrylate copolymer powders        sold under the name Techpolymer ACP-8C by the company Sekisui        Plastics;    -   the expanded hollow particles of acrylonitrile (co)polymer sold        under the name Expancel by the company Expancel;    -   and a mixture or mixtures thereof.

The polymethyl methacrylates are generally in the form of hollow orfilled white spherical particles of which the number-average size D50 isgenerally on the micrometer scale, and in particular ranges from 5 to 20microns and generally ranges from 7 to 15 microns.

As a non-limiting illustration of the polymethyl methacrylates that aresuitable for the invention, mention may particular be made of thepolymethyl methacrylate particles sold by the company Wackherr under thename Covabead LH 85 and those sold by the company Nihon Junyaku underthe name Jurymer MB1.

The expanded hollow particles of acrylonitrile (co)polymer are thusderived from at least one acrylonitrile polymer or copolymer. They aremade of any expanded acrylonitrile polymer or copolymer, which isnon-irritant to the skin.

These particles are advantageously spherical in shape. The density ofthe particles is chosen in the range from 15 kg/m³ to 200 kg/m³, betterstill from 30 kg/m³ to 120 kg/m³ and even better still from 40 kg/m³ to80 kg/m³. To obtain this low density, use is advantageously made ofexpanded polymer or copolymer particles, based on acrylonitrile andpreferably on an acrylic or styrene and/or vinylidene chloride monomer.

It is possible, for example, to use a copolymer containing: from 0% to60% of units derived from vinylidene chloride, from 20% to 90% of unitsderived from acrylonitrile and 0% to 50% of units derived from anacrylic or styrene monomer, the sum of the percentages (by weight) beingequal to 100%. The acrylic monomer is, for example, a methyl or ethylacrylate or methacrylate. The styrene monomer is, for example,methylstyrene or styrene.

Preferably, the particles used in the present invention are hollowparticles of an expanded copolymer of vinylidene chloride andacrylonitrile, an expanded copolymer of vinylidene chloride,acrylonitrile and methacrylate, or a mixture thereof. These particlesmay be dry or hydrated.

The particles of the invention may be obtained, for example, accordingto the processes of patents and patent applications EP-56219, EP-348372, EP-486 080, EP-320 473, EP-112 807 and U.S. Pat. No. 3,615,972.

The internal cavity of the particles contains in principle a gas whichmay be air, nitrogen or a hydrocarbon such as isobutane or isopentane,preferably isobutane.

Advantageously, the particles of the invention have a particle sizeranging from 1 μm to 80 μm, better still ranging from 10 μm to 50 μm andbetter still from 20 μm to 40 μm.

The particles that may be used in the invention are, for example,microspheres of expanded terpolymer of vinylidene chloride,acrylonitrile and methacrylate, sold under the brand name Expancel bythe company Expancel under the references 551 DE 40 (particle size ofapproximately 40 μm), 551 DE 20 (particle size of approximately 20 μmand density of approximately 65 kg/m³), 551 DE 12 (particle size ofapproximately 12 μm), 551 DE 80 (particle size of approximately 80 μm)and 461 DE 50 (particle size of approximately 50 μm). It is alsopossible to use microspheres formed from the same expanded terpolymerwith a particle size of approximately 18 μm and a density ofapproximately 70 kg/m³, referred to below as EL23, or with a particlesize of approximately 34 μm and a density of approximately 20 kg/m³,referred to below as EL 43.

The expanded acrylonitrile (co)polymer hollow particles are preferablychosen from an expanded copolymer of vinylidene chloride andacrylonitrile, an expanded copolymer of vinylidene chloride,acrylonitrile and methacrylate, and a mixture thereof.

Polyurethane Powders

The polyurethane powder is advantageously a hexamethylenediisocyanate/trimethylol hexyl lactone copolymer powder.

Advantageously, the composition according to the invention contains apolyurethane powder that is not film-forming, i.e. it does not form acontinuous and cohesive deposit when it is deposited onto a support suchas the skin.

Such a polyurethane powder is in particular sold under the names PlasticPowder D-400, Plastic Powder D-800 and Plastic Powder T-75 by thecompany Toshiki.

Another polyurethane powder that may be used is the one sold under thename Plastic Powder CS-400 by the company Toshiki.

Silicone Powders

The silicone powder(s) is (are) advantageously chosen from apolymethylsilsesquioxane powder, an organopolysiloxane elastomer powdercoated with silicone resin, and a powder of organosilicone particles.

Polymethylsilsesquioxane Powder

The composition according to the invention comprises at least onesilicone filler and preferably this silicone filler is apolymethylsilsesquioxane powder.

As polymethylsilsesquioxane powder, use may be made of the product soldunder the name Tospearl by the company Momentive Performance Materials,and in particular under the reference Tospearl 145 A.

Organopolysiloxane Elastomer Powder Coated with Silicone Resin

The composition according to the invention comprises at least oneorganopolysiloxane elastomer powder coated with silicone resin, inparticular silsesquioxane resin, as described, for example, in U.S. Pat.No. 5,538,793, the content of which is incorporated by way of reference.

Such elastomer powders are sold under the names KSP-100, KSP-101,KSP-102, KSP-103, KSP-104 and KSP-105 by the company Shin-Etsu, and havethe INCI name: vinyl dimethicone/methicone silsesquioxane crosspolymer.

Preferably, the organopolysiloxane elastomer powder coated with siliconeresin is a compound having the INCI name: Vinyl Dimethicone/MethiconeSilsesquioxane Crosspolymer.

Mention may be made, as silicone elastomer powder, of the powders soldunder the names Trefil® Powder E-505C and Trefil® Powder E-506C by thecompany Dow Corning.

Organosilicone Particles

According to one particular embodiment of the invention, “bowl”-shapedhollow sphere portions are used. Said sphere portions can be obtained asdescribed in application JP-2003 128 788, and horseshoe-shaped hollowsphere portions are also described in application JP-A-2000-191789, orelse in application EP 1 579 841.

As concave particles of sphere portions that may be used according tothe invention, mention may in particular be made of:

-   -   bowl-shaped particles consisting of the crosslinked        organosilicone Tak-110 (methylsilanol/silicate crosslinked        polymer) from the company Takemoto Oil & Fat, of width 2.5 μm,        height 1.2 μm and thickness 150 nm (particles sold under the        name NLK-506 by the company Takemoto Oil & Fat);    -   bowl-shaped particles consisting of the crosslinked        organosilicone Tak-110 (methylsilanol/silicate crosslinked        polymer) from the company Takemoto Oil & Fat, of width 2.5 μm,        height 1.5 μm and thickness 350 nm;    -   bowl-shaped particles consisting of the crosslinked        organosilicone Tak-110 (methylsilanol/silicate crosslinked        polymer) from the company Takemoto Oil & Fat, of width 0.7 μm,        height 0.35 μm and thickness 100 nm;    -   bowl-shaped particles consisting of the crosslinked        organosilicone Tak-110 (methylsilanol/silicate crosslinked        polymer) from the company Takemoto Oil & Fat, of width 7.5 μm,        height 3.5 μm and thickness 200 nm.

Polyamide Powders

Preferably, the polyamide particles have a number-average size rangingfrom 50 nm to 350 microns, better still between 100 nm and 100 micronsand even more preferentially between 0.5 and 100 microns.

The polyamide particles are chosen from particles of nylon 12.

As polyamide powder, mention may also be made of the nylon powders soldunder the name Orgasol® 2002 EXS NAT COS by the company Arkema.

Colorants

The compositions in accordance with the invention comprise at least onecolorant.

This (or these) colorant(s) is (are) preferably chosen from pulverulentmaterials, liposoluble dyes and water-soluble dyes, and mixturesthereof.

Preferably, the compositions according to the invention comprise atleast one pulverulent colorant. The pulverulent colorants may be chosenfrom pigments and nacres, and preferably from pigments.

The pigments may be white or coloured, inorganic and/or organic, andcoated or uncoated. Among the inorganic pigments, mention may be made ofmetal oxides, in particular titanium dioxide, optionallysurface-treated, zirconium, zinc or cerium oxide, and also iron,titanium or chromium oxide, manganese violet, ultramarine blue, chromiumhydrate and ferric blue. Among the organic pigments that may bementioned are carbon black, pigments of D&C type and lakes based oncochineal carmine or on barium, strontium, calcium or aluminium.

The nacres may be chosen from white nacreous pigments such as micacoated with titanium or with bismuth oxychloride, coloured nacreouspigments such as titanium mica with iron oxides, titanium mica with inparticular ferric blue or chromium oxide, titanium mica with an organicpigment of the abovementioned type, and also nacreous pigments based onbismuth oxychloride.

The liposoluble dyes are, for example, Sudan Red, D&C Red 17, D&C Green6, β-carotene, soybean oil, Sudan Brown, D&C Yellow 11, D&C Violet 2,D&C Orange 5, quinoline yellow and annatto.

Preferably, the pigments contained in the compositions according to theinvention are chosen from metal oxides.

These colorants may be present in a content ranging from 0.01% to 30% byweight relative to the total weight of the composition and in particularfrom 6% to 22% by weight relative to the total weight of thecomposition.

Preferably, the colorant(s) is (are) chosen from one or more metaloxides that are present in a content of greater than or equal to 2% byweight relative to the total weight of the composition, andadvantageously inclusively between 6% and 22% by weight relative to thetotal weight of the composition.

Wax(es)

The wax(es) is (are) generally a lipophilic compound that is solid atambient temperature (25° C.), with a solid/liquid reversible change ofstate, having a melting point of greater than or equal to 30° C., whichmay be up to 200° C. and in particular up to 120° C.

For the purposes of the invention, the melting point corresponds to thetemperature of the most endothermic peak observed on thermal analysis(DSC) as described in standard ISO 11357-3; 1999. The melting point ofthe wax may be measured using a differential scanning calorimeter (DSC),for example the calorimeter sold under the name DSC Q2000 by the companyTA Instruments.

Preferably, the waxes have a heat of fusion ΔHf of greater than or equalto 70 J/g.

Preferably, the waxes comprise at least one crystallizable part, whichis for example visible by X-ray observation.

The measurement protocol is as follows:

A 5 mg sample of wax placed in a crucible is subjected to a firsttemperature increase from −20° C. to 100° C., at a heating rate of 10°C./minute, and then is cooled from 120° C. to −20° C. at a cooling rateof 10° C./minute and finally subjected to a second temperature increasefrom −20° C. to 120° C. at a heating rate of 5° C./minute. During thesecond temperature increase, the following parameters are measured:

the melting point (Mp) of the wax, as mentioned previously correspondingto the temperature of the most endothermic peak of the melting curveobserved, representing the variation of the difference in power absorbedas a function of the temperature,

ΔHf: the heat of fusion of the wax, corresponding to the integral entiremelting curve obtained. This heat of fusion of the wax is the amount ofenergy required to make the compound change from the solid state to theliquid state. It is expressed in J/g.

The wax(es) may be hydrocarbon-based wax(es), fluoro wax(es) and/orsilicone wax(es) and may be of plant, mineral and/or synthetic origin.

When present, the wax(es) is (are) present in a total content preferablyof strictly less than 10% by weight, better still less than 5% byweight, or even less than 2% by weight, relative to the total weight ofthe composition.

Hard Wax

The composition may comprise at least one hard wax.

For the purposes of the present invention, the term “hard wax” isintended to mean a wax with a melting point ranging from 65 to 120° C.and more preferentially between 70 and 100° C.

Advantageously, for the purposes of the present invention, the term“hard” wax is intended to mean a wax having, at 20° C., a hardness ofgreater than 5 MPa, in particular ranging from 5 to 30 MPa, preferablygreater than 6 MPa and better still ranging from 6 to 25 MPa.

To take these hardness measurements, the wax is melted at a temperatureequal to the melting point of the wax+20° C. To do this, 30 g of wax areplaced in a 100 ml beaker 50 mm in diameter, which is itself placed on amagnetic-stirring hotplate.

An amount of about 15 g of molten wax is poured into a stainless-steelcontainer 80 mm in diameter and 15 mm deep preheated to 45° C. in anoven. The wax is then left to recrystallize in a room thermostaticallymaintained at 20° C. for 24 hours before taking the measurement.

The mechanical properties of the wax or of the mixture of waxes aredetermined in a room thermostatically maintained at 20° C., using thetexturometer sold under the name TA-XT2i by the company Swantech,equipped with a stainless-steel cylinder 2 mm in diameter.

The measurement comprises three steps: a first step after automaticdetection of the surface of the sample, where the spindle moves at ameasuring speed of 0.1 mm/s, and penetrates into the wax to apenetration depth of 0.3 mm, and the software notes the maximum forcevalue reached; a second “relaxation” step where the spindle remains atthis position for one second and the force is noted after 1 second ofrelaxation; finally, a third “withdrawal” step in which the spindlereturns to its initial position at a speed of 1 mm/s, and the probewithdrawal energy (negative force) is noted.

The hardness value corresponds to the maximum measured compression forcein newtons divided by the area of the texturometer cylinder, expressedin mm², in contact with the wax. The hardness value obtained isexpressed in megapascals or MPa.

As examples of hard wax, mention may be made in particular of carnaubawax, candelilla wax, the wax Bis-PEG-12 Dimethicone Candelillate, forinstance Siliconyl Candelilla Wax sold by the company Koster Keunen,hydrogenated jojoba wax, for instance the product sold by the companyDesert Whale, hydrogenated palm oil such as the product sold by thecompany SIO, rice bran wax, sumach wax, ceresin waxes, laurel wax,Chinese insect wax, shellac wax, hydrogenated olive oil such as Waxolivefrom the company Soliance, the waxes obtained by hydrogenation of oliveoil esterified with C12 to C18 fatty-chain alcohols, such as theproducts sold by the company Sophim under the trade names Phytowax Olive12L44, 14L48, 16L55 and 18L57, the waxes obtained by hydrogenation ofcastor oil esterified with cetyl or behenyl alcohol, for instance theproducts sold under the names Phytowax Ricin 16L64 and Phytowax Ricin22L73 by the company Sophim, hydrogenated camellina wax, ouricury wax,montan wax, ozokerite waxes, for instance Wax SP 1020 P sold by thecompany Strahl & Pitsch, microcrystalline waxes, for instance theproduct sold under the trade name Microwax HW by the company Paramelt,lauric, palmitic, cetylic and stearic acid triglycerides (INCI name:hydrogenated cocoyl glycerides), for instance the product sold under thetrade name Softisan 100 by the company Sasol, polymethylene waxes, forinstance the product sold under the trade name Cirebelle 303 by thecompany Sasol, polyethylene waxes, for instance the products sold underthe trade names Performalene 400 polyethylene, Performalene 655polyethylene and Performalene 500-L polyethylene by the company NewPhase Technologies, alcohol-polyethylene waxes, for instance the productsold under the name Performacol 425 Alcohol by the company Bareco, the95/5 ethylene/acrylic acid copolymer sold under the trade name Wax AC540 by the company Honeywell, hydroxyoctacosanyl hydroxystearate, forinstance the product sold under the trade name Elfacos C 26 by thecompany Akzo, octacosanyl stearate, for instance the product sold underthe name Kester Wax K 82 H by the company Koster Keunen, stearylstearate, for instance the product sold under the name Liponate SS bythe company Lipo Chemicals, pentaerythrityl distearate, for instance theproduct sold under the name Cutina PES by the company Cognis, themixture of dibehenyl adipate, dioctadecyl adipate and dieicosanyladipate (INCI name: C18-22 dialkyl adipate), the mixture of dilauryladipate and ditetradecyl adipate (INCI name: C12-14 dialkyl adipate),the mixture of dioctadecyl sebacate, didocosyl sebacate and dieicosylsebacate (INCI name: C18-22 dialkyl sebacate), the mixture ofdioctadecyl octadecanedioate, didocosyl octanedioate and dieicosyloctanedioate (INCI name: C18-22 dialkyl octanedioate, for instance theproducts sold by the company Cognis, pentaerythrityl tetrastearate, forinstance Liponate PS-4 from the company Lipo Chemicals, tetracontanylstearate, for instance Kester Wax K76 H from the company Koster Keunen,stearyl benzoate, for instance Finsolv 116 from the company Finetex,behenyl fumarate, for instance Marrix 222 from the company Akzo Bernel,bis(1,1,1-trimethylolpropane) tetrastearate, for instance the productoffered under the name Hest 2T-4S by the company Heterene,didotriacontanyl distearate, for instance Kester Wax K82D from thecompany Koster Keunen, polyethylene glycol montanate containing 4oxyethylene units (PEG-4), for instance the product sold under the tradename Clariant Licowax KST1, hexanediol disalicylate, for instanceBetawax RX-13750 sold by the company CP Hall, dipentaerythritylhexastearate, for instance the product sold under the trade name Hest2P-6S by the company Heterene, ditrimethylolpropane tetrabehenate, forinstance the product sold under the trade name Hest 2T-4B by the companyHeterene, jojoba esters, for instance the product sold under the tradename Floraester HIP by the company Floratech, mixtures of linearcarboxylic acid (020-40)/saturated hydrocarbons (INCI name: C20-40 acidpolyethylene), for instance Performacid 350 acid from the company NewPhase Technologies, synthetic wax of Fischer-Tropsch type, such as theproduct sold under the reference Rosswax 100 by the company Ross,stearyl alcohol, behenyl alcohol, dioctadecyl carbonate, for instanceCutina KE 3737, sucrose polybehenate, for instance Crodaderm B from thecompany Croda, and mixtures thereof.

Use may also be made of the waxes mentioned above in the form ofcommercially available mixtures, for example under the names KosterKPC-56 (mixture of 87.5% by weight of cetyl stearate, 7.5% by weight ofbehenyl alcohol and 5% by weight of palm kernel glycerides), KPC-60(mixture of 87.5% by weight of stearyl stearate, 7.5% by weight ofbehenyl alcohol and 5% by weight of palm kernel glycerides), KPC-63(mixture of 87.5% by weight of behenyl stearate, 7.5% by weight ofbehenyl alcohol and 5% by weight of palm kernel glycerides) and KPC-80(mixture of 86% by weight of synthetic beeswax, 7.5% of hydrogenatedplant oil and 6.5% by weight of behenyl alcohol) from the company KosterKeunen.

Use is preferably made of waxes of plant origin such as carnauba wax,candelilla wax, hydrogenated jojoba wax, sumach wax, the waxes obtainedby hydrogenation of olive oil esterified with C12 to C18 fatty-chainalcohols sold by the company Sophim in the Phytowax range (12L44, 14L48,16L55 and 18L57), rice bran wax, stearyl and behenyl alcohols, laurelwax or ouricury wax.

The hard wax(es) is (are) preferably polar.

The term “polar” wax is intended to mean a wax whose solubilityparameter calculated above its melting point δ_(a) is other than 0(J/cm³)^(1/2).

In particular, the term “polar wax” is intended to mean a wax whosechemical structure is formed essentially from, or even constituted of,carbon and hydrogen atoms, and comprising at least one highlyelectronegative heteroatom such as an oxygen, nitrogen, silicon orphosphorus atom.

The definition and calculation of the solubility parameters in theHansen three-dimensional solubility space are described in the articleby C. M. Hansen: “The three dimensional solubility parameters” J. PaintTechnol. 39, 105 (1967).

According to this Hansen space:

-   -   δ_(D) characterizes the London dispersion forces derived from        the formation of dipoles induced during molecular impacts;    -   δ_(p) characterizes the Debye interaction forces between        permanent dipoles and also the Keesom interaction forces between        induced dipoles and permanent dipoles;    -   δ_(h) characterizes the specific interaction forces (such as        hydrogen bonding, acid/base, donor/acceptor, etc.); and    -   δ_(a) is determined by the equation: δ_(a)=(δ_(p) ²+δ_(h)        ²)^(1/2)

The parameters δ_(p), δ_(h), δ_(D) and δ_(a) are expressed in(J/cm³)^(1/2).

When a composition according to the invention comprises at least onehard wax, the total content of hard wax(es) is preferably strictly lessthan 10% by weight, better still less than 5% by weight, or even lessthan 2% by weight, relative to the total weight of the composition.

According to one advantageous embodiment, the composition according tothe invention is free of hard wax(es).

A composition according to the invention may comprise at least one softwax, i.e. of which the melting point is strictly less than 50° C., andoptionally of which the hardness is strictly less than 5 MPa.

However, a composition according to the invention preferably comprisesless than 10% by weight of soft wax(es), preferably less than 5% byweight of soft wax(es), or even less than 2% by weight of soft wax(es),and even more preferentially is free of soft wax(es).

Gelling Agents

Hydrophilic Gelling Agents

The compositions according to the present invention may also contain atleast one hydrophilic, or water-soluble, gelling agent, which may bechosen from:

-   -   acrylic or methacrylic acid homopolymers or copolymers or the        salts thereof and esters thereof and in particular the products        sold under the names Versicol F® or Versicol K® by the company        Allied Colloid, Ultrahold 8® by the company Ciba-Geigy, and        polyacrylic acids of Synthalen K type,    -   copolymers of acrylic acid and of acrylamide sold in the form of        the sodium salt thereof under the names Reten® by the company        Hercules, and the sodium salts of polyhydroxycarboxylic acids        sold under the name Hydagen F® by the company Henkel,    -   polyacrylic acid/alkyl acrylate copolymers of Pemulen type;    -   AMPS (polyacrylamidomethylpropanesulfonic acid partially        neutralized with aqueous ammonia and highly crosslinked) sold by        the company Clariant,    -   AMPS/acrylamide copolymers of Sepigel® or Simulgel® type sold by        the company SEPPIC, and    -   AMPS/polyoxyethylenated alkyl methacrylate copolymers        (crosslinked or non-crosslinked), and mixtures thereof.    -   associative polymers and in particular associative polyurethanes        such as the C₁₆-OE₁₂₀-C₁₆ polymer from the company Elementis        (sold under the name Rheolate FX1100, this molecule bearing a        urethane function and having a weight-average molecular weight        of 1300), OE being an oxyethylene unit, Rheolate 205 bearing a        urea function, sold by the company Rheox, or also Rheolate 208        or 204 (these polymers being sold in pure form) or DW 1206B from        Röhm & Haas bearing a C₂₀ alkyl chain and a urethane bond, sold        at 20% solids in water. It is also possible to use solutions or        dispersions of these associative polyurethanes, in particular in        water or in aqueous-alcoholic medium. Examples of such polymers        that may be mentioned include Rheolate FX1010, Rheolate FX1035,        Rheolate1070, Rheolate 255, Rheolate 278 and Rheolate 244 sold        by the company Elementis. It is also possible to use the        products DW 1206F and DW 1206J, and also Acrysol RM 184 or        Acrysol 44 from the company Röhm & Haas, or alternatively        Borchigel LW 44 from the company Borchers,    -   and mixtures thereof.

Some water-soluble film-forming polymers also act as water-solublegelling agent.

The hydrophilic gelling agents may be present in the compositionsaccording to the invention in a content ranging from 0.05% to 10% byweight, preferably from 0.1% to 5% by weight and better still from 0.5%to 2% by weight, relative to the total weight of the composition.

A composition according to the invention advantageously comprises one ofthe abovementioned gelling agents, preferably chosen from AMPS(polyacrylamidomethylpropanesulfonic acid partially neutralized withammonia and highly crosslinked), AMPS/acrylamide copolymers, and amixture thereof.

Lipophilic Gelling Agents

A composition according to the invention may comprise at least onelipophilic or liposoluble gelling agent.

The gelling agent(s) that may be used may be organic or mineral,polymeric or molecular lipophilic gelling agents.

Mineral lipophilic gelling agents that may be mentioned include clays,modified clays, such as Bentone 38 VCG by the company Elementis, andoptionally hydrophobically surface-treated fumed silica.

The polymeric organic lipophilic gelling agents are, for example,partially or completely crosslinked elastomeric organopolysiloxanes ofthree-dimensional structure, such as the products sold under the namesKSG6®, KSG16® and KSG18® by the company Shin-Etsu, TREFIL E-5050® andTrefil E-506C® by the company Dow Corning, Gransil SR-CYC®, SR DMF10®,SR-DC556®, SR 5CYC Gel®, SR DMF 10 Gel® and SR DC 556 Gel® by thecompany Grant Industries and SF 1204® and JK 113® by the company GeneralElectric; ethyl cellulose, such as the product sold under the nameEthocel® the company by Dow Chemical; polycondensates of polyamide typeresulting from the condensation between (α) at least one acid chosenfrom dicarboxylic acids containing at least 32 carbon atoms, such asfatty acid dimers, and (β) an alkylenediamine and in particularethylenediamine, in which the polyamide polymer comprises at least onecarboxylic acid end group esterified or amidated with at least onesaturated and linear monoalcohol or monoamine containing from 12 to 30carbon atoms, and in particular ethylenediamine/stearyl dilinoleatecopolymers such as the product sold under the name Uniclear 100 VG® bythe company Arizona Chemical; silicone polyamides of thepolyorganosiloxane type such as those described in documents U.S. Pat.Nos. 5,874,069, 5,919,441, 6,051,216 and 5,981,680, for instance theproducts sold under the references Dow Corning 2-8179 and Dow Corning2-8178 Gellant by the company Dow Corning. Block copolymers of“diblock”, “triblock” or “radial” type, of the polystyrene/polyisopreneor polystyrene/polybutadiene type, such as the products sold under thename Luvitol HSB® by the company BASF, of thepolystyrene/copoly(ethylene-propylene) type, such as the products soldunder the name Kraton® by the company Shell Chemical Co., or also of thepolystyrene/copoly(ethylene-butylene) type, and mixtures of triblock andradial (star) copolymers in isododecane, such as the products sold bythe company Penreco under the name Versagel®, for instance the mixtureof butylene/ethylene/styrene triblock copolymer and ofethylene/propylene/styrene star copolymer in isododecane (Versagel M5960).

The compositions according to the invention may also comprise anon-emulsifying silicone elastomer as lipophilic gelling agent. Amongthe lipophilic gelling agents that may also be mentioned areorganogelling agents.

A composition according to the invention is preferably free oflipophilic gelling agent.

Cosmetic Active Agents

The compositions in accordance with the invention may also comprise atleast one cosmetic active agent.

As cosmetic active agents that may be used in the compositions inaccordance with the invention, mention may be made in particular ofantioxidants, preserving agents, fragrances, neutralizers, emollients,coalescers, moisturizers, vitamins and screening agents, in particularsunscreens, and mixtures thereof.

Needless to say, those skilled in the art will take care to select theoptional additional ingredients and/or the amount thereof such that theadvantageous properties of the composition according to the inventionare not, or are not substantially, adversely affected by the envisagedaddition.

Preferably, the composition according to the invention is a leave-incomposition. Advantageously, the composition is a makeup composition andin particular a mascara.

Oil or Organic Solvent

The compositions according to the invention may comprise at least oneoil or organic solvent.

The compositions according to the invention may in particular compriseat least one oil chosen from at least one non-volatile oil, at least onevolatile oil, and a mixture thereof.

Non-Volatile Oil

The term “oil” is intended to mean a fatty substance that is liquid atambient temperature and at atmospheric pressure.

The term “non-volatile oil” is intended to mean an oil that remains onthe skin or the keratin fibre at ambient temperature and pressure. Moreprecisely, a non-volatile oil has an evaporation rate strictly less than0.01 mg/cm²/min.

To measure this evaporation rate, 15 g of oil or of oil mixture to betested are placed in a crystallizing dish 7 cm in diameter, which isplaced on a balance in a large chamber of about 0.3 m³ that istemperature-regulated, at a temperature of 25° C., andhygrometry-regulated, at a relative humidity of 50%. The liquid isallowed to evaporate freely, without stirring it, while providingventilation by means of a fan (Papst-Motoren, reference 8550 N, rotatingat 2700 rpm) placed in a vertical position above the crystallizing dishcontaining said oil or said mixture, the blades being directed towardsthe crystallizing dish, 20 cm away from the bottom of the crystallizingdish. The mass of oil remaining in the crystallizing dish is measured atregular intervals. The evaporation rates are expressed in mg of oilevaporated per unit of area (cm²) and per unit of time (minutes).

Said at least one non-volatile oil may be chosen from hydrocarbon-basedoils and silicone oils, and mixtures thereof, preferably fromhydrocarbon-based oils.

The non-volatile hydrocarbon-based oils that are suitable for thepresent invention may be chosen in particular from:

-   hydrocarbon-based oils of plant origin, such as triglycerides    consisting of fatty acid esters of glycerol, the fatty acids of    which may have chain lengths ranging from C4 to C28, these fatty    acids possibly being linear or branched, and saturated or    unsaturated; these oils are in particular wheatgerm oil, sunflower    oil, grapeseed oil, sesame oil, corn oil, apricot oil, castor oil,    shea oil, avocado oil, olive oil, soybean oil, sweet almond oil,    rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba    oil, palm oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil,    blackcurrant oil, evening primrose oil, millet oil, barley oil,    quinoa oil, rye oil, safflower oil, candlenut oil, passion flower    oil and musk rose oil; or alternatively caprylic/capric acid    triglycerides such as those sold by the company Stéarineries Dubois    or those sold under the names Miglyol 810®, 812® and 818® by the    company Sasol;-   synthetic ethers containing from 10 to 40 carbon atoms;-   linear or branched hydrocarbons of mineral or synthetic origin other    than the polymers according to the invention, such as petroleum    jelly, polybutenes, polydecenes and squalane, and mixtures thereof;-   synthetic esters such as the oils of formula R1COOR2 in which R1    represents the linear or branched fatty acid residue containing from    1 to 40 carbon atoms and R2 represents an in particular branched    hydrocarbon-based chain containing from 1 to 40 carbon atoms, on    condition that R1+R2≥10, for instance purcellin oil (cetostearyl    octanoate), isopropyl myristate, isopropyl palmitate, C12 to C15    alkyl benzoate, hexyl laurate, diisopropyl adipate, isononyl    isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, alkyl    or polyalkyl octanoates, decanoates or ricinoleates such as    propylene glycol dioctanoate; hydroxylated esters such as    isostearate lactate and diisostearyl malate; and pentaerythritol    esters;-   fatty alcohols that are liquid at ambient temperature, with a    branched and/or unsaturated carbon-based chain containing from 12 to    26 carbon atoms, for instance octyldodecanol, isostearyl alcohol,    oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and    2-undecylpentadecanol; and-   higher fatty acids such as oleic acid, linoleic acid or linolenic    acid, and mixtures thereof.

The non-volatile silicone oils that are suitable for the presentinvention may be chosen in particular from:

-   the non-volatile silicone oils that may be used in the composition    in accordance with the invention may be non-volatile    polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising    alkyl or alkoxy groups, that are pendent and/or at the end of a    silicone chain, the groups each containing from 2 to 24 carbon    atoms, phenyl silicones, such as phenyl trimethicones, phenyl    dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl    dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl    trimethylsiloxysilicates.

A composition according to the invention optionally comprises at leastone non-volatile hydrocarbon-based oil of plant origin, such astriglycerides consisting of fatty acid esters of glycerol the fattyacids of which may have chain lengths ranging from C4 to C28, inparticular palm oil and hydrogenated jojoba oil. A composition accordingto the invention is preferably free of silicone non-volatile oil(s).

A composition according to the invention is preferably free ofnon-volatile oil. However, the total content of non-volatile oil(s) in acomposition in accordance with the invention may range from 0.01% to 10%by weight, in particular from 0.1% to 8% by weight and preferably from0.25% to 5% by weight relative to the total weight of the composition.

According to one preferred embodiment, a composition according to theinvention comprises less than 5% by weight of non-volatile oil(s)relative to the total weight of the composition.

Volatile Oil

The composition according to the invention may comprise at least onevolatile oil.

The term “volatile oil” is intended to mean an oil (or non-aqueousmedium) that can evaporate on contact with the skin in less than onehour, at ambient temperature and atmospheric pressure. The volatile oilis a cosmetic volatile oil, which is liquid at ambient temperature. Morespecifically, a volatile oil has an evaporation rate of between 0.01 and200 mg/cm²/min, limits included.

This volatile oil may be hydrocarbon-based.

The volatile hydrocarbon-based oil may be chosen from hydrocarbon-basedoils containing from 7 to 16 carbon atoms.

The composition according to the invention may contain one or morevolatile branched alkanes. The expression “one or more volatile branchedalkanes” is intended to mean, without preference, “one or more volatilebranched alkane oils”.

As a volatile hydrocarbon-based oil containing from 7 to 16 carbonatoms, mention may be made in particular of C8-C16 branched alkanes,such as C8-C16 isoalkanes (also known as isoparaffins), isododecane,isodecane, isohexadecane and for example the oils sold under the tradenames Isopar or Permethyl, C8-C16 branched esters such as isohexylneopentanoate, and mixtures thereof. Preferably, the volatilehydrocarbon-based oil containing from 8 to 16 carbon atoms is chosenfrom isododecane, isodecane and isohexadecane, and mixtures thereof, andis in particular isododecane.

The composition according to the invention may contain one or morevolatile linear alkanes. The term “one or more volatile linear alkanes”is intended to mean, without preference, “one or more volatile linearalkane oils”.

A volatile linear alkane that is suitable for the invention is liquid atambient temperature (about 25° C.) and at atmospheric pressure (760mmHg).

A “volatile linear alkane” that is suitable for the invention isintended to mean a cosmetic linear alkane, which is capable ofevaporating on contact with the skin in less than one hour, at ambienttemperature (25° C.) and atmospheric pressure (760 mmHg, i.e. 101 325Pa), which is liquid at ambient temperature, in particular having anevaporation rate ranging from 0.01 to 15 mg/cm²/min, at ambienttemperature (25° C.) and atmospheric pressure (760 mmHg).

The linear alkanes, preferably of plant origin, comprise from 7 to 15carbon atoms, in particular from 9 to 14 carbon atoms and moreparticularly from 11 to 13 carbon atoms.

As examples of linear alkanes that are suitable for the invention,mention may be made of the alkanes described in patent applications WO2007/068 371 or WO 2008/155 059 by the company Cognis (mixtures ofdistinct alkanes that differ by at least one carbon). These alkanes areobtained from fatty alcohols, which are themselves obtained from coconutoil or palm oil.As examples of linear alkanes that are suitable for the invention,mention may be made of n-heptane (C7), n-octane (C8), n-nonane (C9),n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13),n-tetradecane (C14) and n-pentadecane (C15), and mixtures thereof, andin particular the mixture of n-undecane (C11) and n-tridecane (C13)described in Example 1 of patent application WO 2008/155 059 by thecompany Cognis. Mention may also be made of n-dodecane (C12) andn-tetradecane (C14) sold by Sasol under the references, respectively,Parafol 12-97 and Parafol 14-97, and also mixtures thereof.The linear alkane may be used alone or as a mixture of at least twodistinct alkanes that differ from each other by a carbon number of atleast 1, and in particular a mixture of at least two linear alkanescomprising from 10 to 14 distinct carbon atoms that differ from eachother by a carbon number of at least 2, and in particular a mixture ofC11/C13 volatile linear alkanes or a mixture of C12/C14 linear alkanes,in particular an n-undecane/n-tridecane mixture (such a mixture may beobtained according to Example 1 or Example 2 of WO 2008/155 059).

As a variant or additionally, the composition prepared may comprise atleast one volatile silicone oil or solvent that is compatible withcosmetic use.

The term “silicone oil” is intended to mean an oil containing at leastone silicon atom, and in particular containing Si—O groups. According toone embodiment, said composition comprises less than 10% by weight ofnon-volatile silicone oil(s), relative to the total weight of thecomposition, better still less than 5% by weight, or even is free ofsilicone oil.

Volatile silicone oils that may be mentioned include cyclicpolysiloxanes and linear polysiloxanes, and mixtures thereof. Volatilelinear polysiloxanes that may be mentioned include hexamethyldisiloxane,octamethyltrisiloxane, decamethyltetrasiloxane,tetradecamethylhexasiloxane and hexadecamethylheptasiloxane. Volatilecyclic polysiloxanes that may be mentioned includehexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.

As a variant or additionally, the composition prepared may comprise atleast one volatile fluoro oil.

The term “fluoro oil” is intended to mean an oil containing at least onefluorine atom.

Volatile fluoro oils that may be mentioned includenonafluoromethoxybutane and perfluoromethylcyclopentane, and mixturesthereof.

A composition according to the invention is preferably free ofnon-volatile oil. However, at least one volatile oil may be present in atotal content ranging from 0.1% to 10% by weight. In particular, thevolatile oil may be present in the composition in a content ranging from0.5% to 5% by weight relative to the total weight of the composition.

According to one preferred embodiment, a composition according to theinvention comprises less than 5% by weight of volatile oil(s) relativeto the total weight of the composition.

Assembly

An assembly for coating keratin fibres suitable for the invention maycomprise an applicator suitable for applying said cosmetic compositionfor coating keratin fibres and, where appropriate, a packaging devicesuitable for receiving said composition.

Applicator

The applicator may comprise means for smoothing and/or separatingkeratin fibres, such as the eyelashes or the eyebrows, in particular inthe form of teeth, bristles or other reliefs.

The applicator is arranged to apply the composition to the eyelashes orthe eyebrows, and may comprise, for example, a brush or a comb.

The applicator may also be used for finishing of the makeup, over aregion of the eyelashes or eyebrows that is made up or laden withcomposition.

The brush may comprise a twisted core and bristles held between theturns of the core, or may be made in yet another way.

The comb is, for example, produced from a single part by moulding of aplastic.

In certain exemplary embodiments, the application member is mounted atthe end of a wand, which wand may be flexible, which may contribute toimproving the comfort during application.

Packaging Device

The packaging device may comprise a container for housing thecomposition for coating keratin fibres. This composition may then bewithdrawn from the container by immersing the applicator therein.

This applicator may be firmly attached to a member for closing thecontainer. This closing member may form a member for gripping theapplicator. This gripping member may form a cap to be removably mountedon said container by any suitable means, such as screwing,click-fastening, coupling, etc. Such a container may thus reversiblyhouse said applicator.

This container may be optionally equipped with a wiper suitable forremoving surplus product taken up by the applicator.

A process for applying the composition according to the invention to theeyelashes or the eyebrows may also include the following steps:

-   forming a deposit of the cosmetic composition on the eyelashes or    the eyebrows,-   leaving the deposit on the eyelashes or the eyebrows, it being    possible for the deposit to dry.

It should be noted that, according to another embodiment, the applicatormay form a product container. In such a case, a container may, forexample, be provided in the gripping member and an internal channel caninternally connect this gripping member to the application members inrelief.

Finally, it should be noted that the packaging and application assemblymay be in the form of a kit, it being possible for the applicator andthe packaging device to be housed separately in the same packagingarticle.

The examples above and that follow are given as illustrations of thepresent invention, and shall not limit the scope thereof.

EXAMPLES

A mascara composition in accordance with the invention is describedbelow:

Composition Comparative Comparative 1 according composition compositionIngredients to the 2 outside the 3 outside the with percentage contentsinvention invention invention STEARETH 2 (Brij S2-SO-(TH) from Croda) 1010 — Sodium stearoyl glutamate (AMISOFT HS 11 PF 10 — — from AJINOMOTO)CETYL PHOSPHATE (AMPHISOL K from DSM — 10 — Nutritional Products)CARNAUBA Wax 16 Peg 30 Glyceryl stearate (TAGAT S from EVONIK)  4ACRYLIC AND STYRENE/ACRYLIC COPOLYMERS 25 25 25 AS A 40% AQUEOUSEMULSION IN A WATER/BUTYLENE GLYCOL/PROTECTED SODIUM LAURYL ETHERSULFATE MIXTURE (SYNTRAN 5760 CG from INTERPOLYMER) Pigments (ironoxides)   12.2   12.2   12.2 Water qs 100 qs 100 qs 100 Preservatives qsqs qs

Composition 1 according to the invention was prepared as follows:

The ingredients are weighed out, the Steareth 2 and sodium stearoylglutamate in accordance with the invention are melted at 80° C., and thewater preheated in an electric kettle to 95° C. and the pigments arethen added. Mixing is carried out for 5 minutes at 95° C. using a Moritzblender. The mixture is left to cool to 60° C., with slow stirring, andthen the dispersion of film-forming polymer is added.

The preservatives are poured into the mixture when the temperature ofthe mixture is less than or equal to 45° C.

The mascara thus obtained is transferred into a closed jar to prevent itfrom drying out on contact with air; it is then necessary to wait 24hours to check the homogeneity of the formulation and the correctdispersion of the pigments.

The same preparation protocol is used for the comparative compositionsoutside the invention.

1/Verification of the Presence of a Lamellar Phase Lβ

The presence of a lamellar phase Lβ was first of all suspected by meansof an optical microscope with cross-polarized light with a magnificationof 10.

It should be noted that the characterization of a lamellar phase Lβusing the X-ray diffraction technique previously explained should becarried out essentially on a combination of surfactant system andaqueous phase in order to avoid any scattering which might mask thelamellar-phase lines, capable of disrupting the measurements. Thus, thismeasurement should be carried out on a composition free of pigments andof fillers. This measurement can be carried out on the followingcompositions:

Composition Comparative 1′ according composition Ingredients to the 2′outside with percentage contents invention the invention STEARETH 2(Brij 72 from Uniqema)  7  7 Sodium stearoyl glutamate (AMISOFT 15 — HS11 PF from AJINOMOTO) CETYL PHOSPHATE (AMPHISOL — 15 K from DSMNutritional Products) Water qs 100 qs 100 Preserving agents qs qs

It should be noted that, although the surfactant contents were slightlymodified compared with the example of composition 1 according to theinvention previously given, a similar, or even identical, X-raydiffraction spectrum would be obtained with the surfactant contents ofsaid composition 1′ free of pigments and of fillers.

Conversely, a surfactant system in which the acyl glutamic acid, or saltthereof, was replaced with an anionic surfactant with an HLB value ofgreater than or equal to 8 chosen from cetyl phosphate, as used incomparative composition 2′ outside the invention, does not allow theformation of a lamellar phase Lβ.

2/Protocols and Results

The composition 1 prepared is observed with the naked eye and under amicroscope, and then tested on a test sample of bare eyelashes, byapplication of these compositions using a brush.

The composition 1 according to the invention exhibits, to the naked eye,a black colour of good intensity and, under a microscope, a finedispersion of particles.

The composition in accordance with the invention is pleasant to apply,it has a fluid texture, the deposit is constructed coat after coat, thecomposition coats the eyelashes well, the makeup result is uniform andthe eyelash fringe is well spread out. In addition, this composition isstable at 4° C. and 45° C. for two months.

Comparative composition 2 outside the invention is less black, lessstable and less uniform under microscopic observation.

Comparative composition 3 outside the invention is too liquid to allow arheological measurement.

The application of composition 1 according to the invention to theeyelashes is more pleasant than that of comparative composition 2outside the invention or that of comparative composition 3 outside theinvention. The playtime of composition 1 according to the invention islonger than that of comparative composition 2 outside the invention orof comparative composition 3 outside the invention, it being greaterthan 20 brushstrokes without impairing the application. Furthermore, thevolume conferred by composition 1 according to the invention is greaterthan that conferred by comparative composition 2 outside the inventionor comparative composition 3 outside the invention.

Comparative Example Outside the Invention Using a Weight Content ofSurfactant System According to the Invention which is Too Low

Comparative composition 4 Ingredients outside the with percentagecontents invention STEARETH 2 (BRIJ S2-SO-(TH) from CRODA) 10 Sodiumstearoyl glutamate (AMISOFT HS 11 PF from  3 AJINOMOTO) Water qs 100

The presence of 13% by weight of a mixture of a surfactant with an HLBat 25° C. of less than 8 and of a surfactant with an HLB at 25° C. ofgreater than or equal to 8 chosen from stearoyl glutamate does not makeit possible to form a lamellar phase, contrary to the compositionsaccording to the invention which comprise at least 15% by weight ofsurfactant system.

It is understood that, in the context of the present invention, theweight percentages given for a compound or a family of compounds arealways expressed as weight of solids of the compound in question.

Throughout the application, the wording “comprising one” or “containingone” means “comprising at least one” or “containing at least one”,unless otherwise specified.

The invention claimed is:
 1. A cosmetic composition for coating akeratin fiber, the composition comprising: an aqueous phase; asurfactant system present at a total content of greater than or equal to15% by weight relative to a total weight of the composition, saidsurfactant system comprising: i) at least one non-ionic surfactant withan HLB value at 25° C. of less than 8, and ii) at least one anionicsurfactant with an HLB value at 25° C. of greater than or equal to 8selected from the group consisting of an acyl glutamic acid and a saltthereof, together forming a lamellar phase Lβ; at least one aqueousdispersion of particles of at least one film-forming polymer; andoptionally one or more waxes which, if present, are present in a waxcontent of less than 5% by weight relative to the total weight of thecomposition.
 2. The composition according to claim 1, wherein the atleast one non-ionic surfactant is represented by formula (I):(ALK-[C(O)]_(a)—[O]_(b))_(c)—X  (I) where: ALK is a C₇-C₂₃ alkyl group,a and b are independently an integer between 0 and 100, c is an integerbetween 1 and 100, X is a (poly)oxyalkylene group optionally substitutedand/or terminated with a hydroxyl group.
 3. The composition according toclaim 2, wherein the group X is: i)HO-(ALK-O)_(z)—CH2—CH[(OALK)_(y)—OH]—CH2-(O-ALK)_(x)-(*) where: ALK isindependently a C1-C6 alkylene group and, x, y and z are independentlyan integer between 0 and 10, with the proviso that x+y+z is other than0; or ii) H-(ALK-O)_(x)-(*) and H-(O-ALK)_(x)-(*), where: ALK isindependently a C1-C6 alkylene group, and x is an integer other than 0.4. The composition according to claim 1, wherein the at least onenon-ionic surfactant is represented by formula (I′):ALK-(O—CH₂—CH₂)_(n)—OH  (I′) where ALK is a C₈-C₂₄ alkyl group, and n isan integer other than
 0. 5. The composition according to claim 1,wherein the at least one non-ionic surfactant is selected from the groupconsisting of: an ester and an ether of a monosaccharide which isoptionally (poly)oxyalkylenated; an ester of a fatty acid, and of apolyol, which is (poly)oxyalkylenated; an alcohol which is optionally(poly)oxyalkylenated; and a mixture thereof.
 6. The compositionaccording to claim 1, wherein the at least one non-ionic surfactantcomprises an alcohol, which is optionally (poly)oxyalkylenated andcomprises an ether of a C₈-C₂₄ fatty alcohol and of polyethylene glycol,said ether comprising from 1 to 10 ethylene glycol units.
 7. Thecomposition according to claim 1, wherein the at least one anionicsurfactant comprises at least one acyl glutamic acid having at least oneC₁₂-C₂₂ acyl chain, a salt thereof, or a mixture thereof.
 8. Thecomposition according to claim 1, wherein the at least one anionicsurfactant is present in a content of greater than or equal to 5% byweight relative to the total weight of the composition.
 9. Thecomposition according to claim 1, wherein the at least one non-ionicsurfactant is present in a content of greater than or equal to 5% byweight relative to the total weight of the composition.
 10. Thecomposition according to claim 1, wherein the at least one non-ionicsurfactant and the at least one anionic surfactant are present in atotal content of greater than or equal to 15% by weight relative to thetotal weight of the composition.
 11. The composition according to claim1, wherein the at least one non-ionic surfactant and the at least oneanionic surfactant are present in a respective total content such that aweight ratio of the at least one non-ionic surfactant to the at leastone anionic surfactant ranges from 1/5 to 5/1.
 12. The compositionaccording to claim 1, wherein the particles of the at least onefilm-forming polymer are radical synthetic polymers, polycondensatesynthetic polymers, polymers of natural origin, or a mixture thereof.13. The composition according to claim 1, wherein the at least oneaqueous dispersion of the particles of the at least one film-formingpolymer is an acrylic polymer dispersion, a polyurethane dispersion, asulfopolyester dispersion, a vinyl dispersion, a polyvinyl acetatedispersion, a vinylpyrrolidone, dimethylaminopropylmethacrylamide andlauryldimethylpropylmethacrylamidoammonium chloride terpolymerdispersion, a dispersion of polyurethane/polyacrylic hybrid polymers, adispersion of core-shell particles, and a mixture thereof.
 14. Thecomposition according to claim 1, wherein the aqueous phase is presentin a content of from 30% to 70% by weight relative to the total weightof the composition.
 15. The composition according to claim 1, whichcomprises a wax content of less than or equal to 2% by weight relativeto the total weight of the composition.
 16. The composition according toclaim 1, comprising at least one colorant, which is at least onepulverulent substance.
 17. The composition according to claim 1, havinga viscosity at 25° C. ranging from 5 to 50 Pa·s.
 18. A process forcoating a keratin fibre, the process comprising applying to the keratinfibre the composition according to claim 1.